1-ethylene-2-alkylene-1,4-cyclohexadiene pesticides

ABSTRACT

Pesticidally active cyclohexadienyl derivative compounds of the formula I that are esters, oximes or amides are claimed. These compounds may be used as fungicides, acaricides and insecticides in plant protection.

This application is a 371 of PCT/EP97/02889 filed Jun. 4, 1997.

The invention relates to novel pesticidally active compounds of formulaI

wherein:

X is CH or N;

Y is O, S, S═O or NR₅;

Z is OR₂, SR₂ or N(R₃)R₄;

n is 0, 1, 2, 3, 4 or 5; or

Y and Z together form a 5- to 7-membered ring containing 2 or 3 heteroatoms O and/or N that is unsubstituted or mono- or poly-substituted byC₁-C₄alkyl, halo-C₁-C₄alkyl, halogen, ═O or by cyclopropyl;

W is an aldimino or ketimino group;

R₁ is cyclopropyl, C₁-C₆alkyl or halo-C₁-C₆-alkyl;

R₂ and R₃ are each independently of the other C₁-C₆alkyl orhalo-C₁-C₆alkyl;

R₄ and R₅ are each independently of the other hydrogen, C₁-C₆alkyl orC₁-C₆alkoxy;

R₈ and R₉ are each independently of the other hydrogen or C₁-C₃alkyl; or

R₈ and R₉ together are C₂-C₆alkenyl or C₃-C₆cycloalkyl;

R₂₁ and R₂₂ are each independently of the other hydrogen, halogen,C₁-C₈alkyl, C₁-C₈alkoxy or C₁-C₈alkylthio; and

R₂₃, R₂₄, R₂₅ and R₂₆ are each independently of the others hydrogen,halogen, C₁-C₈alkyl or C₁-C₈alkoxy.

Formula I includes all stereoisomeric forms and also mixtures thereof,such as racemic and diastereoisomeric mixtures, for example E/Zmixtures.

The compounds of the invention have fungicidal, acaricidal andinsecticidal properties and are suitable for use as active ingredientsin agriculture, horticulture and in the hygiene sector.

The invention relates also to the preparation of those compounds, toagrochemical compositions that comprise at least one of those compoundsas active ingredient, and to the use of the active ingredients orcompositions in the protection of plants against attack by harmfulmicroorganisms as well as in the control of insects.

2-Alkoximino-2-phenylacetic acid derivatives and2-alkoxymethylene-2-phenylacetic acid derivatives are known aspesticides, for example, from WO 94/26700 and WO 95/18789. Correspondingpesticidal compounds in which a cyclohexenyl group stands in place ofthe phenyl group are described in EP-A-421 102, and those in which thephenyl group has been replaced by a cyclohexyl group are described inEP-A-438 726. In addition, the phytofungicidal action of1,4-cyclohexadiene-1-alanine is described in J. of Antibiotics, Vol.XXIII, No.11, p. 537-541 (1970).

The general terms used hereinbefore and hereinafter have the meaningsgiven below unless specified otherwise:

Hydrocarbon radicals may be saturated or unsaturated, open-chained orcyclic, or a mixture of open-chained and cyclic such as, for example,cyclopropylmethyl or benzyl.

Alkyl groups are straight-chain or branched, depending on the number ofcarbon atoms, and are, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, sec-amyl, tert-amyl, 1-hexylor 3-hexyl.

Unsaturated hydrocarbon radicals are alkenyl, alkynyl or alkenynylgroups having a maximum of 3 multiple bonds, such as, for example,butadienyl, hexatrienyl or 2-penten-4-ynyl.

Alkenyl is to be understood as meaning straight-chain or branchedalkenyl, such as, for example, allyl, methallyl, 1-methylvinyl orbut-2-en-1-yl. Alkenyl radicals having a chain length of 3 or 4 carbonatoms are preferred.

Alkynyl may similarly, depending on the number of carbon atoms, bestraight-chain or branched, such as, for example, ethynyl, propargyl,but-1-yn-1-yl or but-1-yn-3-yl. Propargyl is preferred.

Cyclic unsaturated hydrocarbon radicals may be aromatic, such as, forexample, phenyl and naphthyl, or non-aromatic, such as, for example,cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctadienyl, orpartially aromatic, such as, for example, tetrahydronaphthyl andindanyl.

Halogen and halo are fluorine, chlorine, bromine or iodine, preferablyfluorine, chlorine or bromine.

Haloalkyl may contain identical or different halogen atoms and may be,for example, fluoromethyl, difluoromethyl, difluorochloromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethylor 3,3,3-trifluoropropyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy,isobutoxy, sec-butoxy or tert-butoxy; preferably methoxy or ethoxy.

Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy,2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy,2-chloroethoxy or 2,2-difluoroethoxy.

Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkanoyl is either straight-chain or branched. Examples are formyl,acetyl, propionyl, butyryl, pivaloyl and octanoyl.

Aryl is phenyl or naphthyl, preferably phenyl.

The term heteroaryl denotes 5- or 6-membered aromatic rings containinghetero atoms N, O and/or S, which may be benzo-fused. Examples arefuran, pyrrole, pyridine, pyrimidine, pyrazine, thiazole, oxazole,isoxazole, isothiazole, triazine, quinoline, isoquinoline, pyridazine,pyrazole, imidazole, quinazoline, quinoxaline, benzimidazole,benzofuran, indole, isoindole, benzothiazole and benzoxazole.

Heterocyclyl denotes 5- to 7-membered, non-aromatic rings that containfrom 1 to 3 identical or different hetero atoms N, O and S. Examples areΔ²-oxazoline, Δ²-thiazoline; 5,6-dihydro-4H-1,3-thiazine,5,6-dihydro-4H-1,3-oxazine, pyrrolidine, indoline, piperidine,morpholine, 4-alkylpiperidine and azepine.

All of the above lists are given by way of example and are not limitingin any way.

The following groups are preferred:

(1) Compounds of formula I wherein:

W is a group a)

wherein

R₁₁ and R₁₂ are each independently of the other hydrogen, cyano,C₁-C₁₂alkyl, halo-C₁-C₁₂-alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl,C₃-C₆cycloalkyl, cyclopropylmethyl, C₁-C₄alkoxy, C₂-C₁₂-alkoxyalkyl,C₁-C₄alkoxycarbonyl, aminocarbonyl, C₁-C₄alkylaminocarbonyl,bis(C₁-C₄alkyl)-aminocarbonyl, ureidocarbonyl, C₁-C₄alkylthio,C₂-C₅alkylthioalkyl; an unsubstituted or up to penta-substituted ringhaving a maximum of 15 ring carbon atoms that may be multi-membered andcontains from 0 to 3 hetero atoms N, O and/or S, it being possible forthe ring to be bonded by a bridge having a maximum of 4 chain atoms andthat may be linear or branched and may contain CO, oxygen or sulfur; or

R₁₁ and R₁₂ together with the common carbon atom are an unsubstituted orup to penta-substituted ring having a maximum of 15 ring carbon atomsthat may be multi-membered and contains from 0 to 3 hetero atoms N, Oand/or S;

the possible substituents of all of those groups mentioned for R₁₁ andR₁₂ individually or together being selected from C₁-C₄alkyl,C₂-C₄alkenyl, C₂-C₄alkynyl, C₁-C₄alkoxy, C₁-C₄alkyl-thio,C₁-C₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₁-C₄haloalkoxy,halogen, cyano, cyano-C₁-C₂alkyl, cyano-C₁-C₂alkoxy, oxo, thioxo, OH,NO₂, SCN, thiocyanomethyl, Si(CH₃)₃, NH₂, NH(C₁-C₄alkyl),N(C₁-C₄alkyl)₂, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylcarbonyl,C₁-C₄haloalkylcarbonyl, C₁-C₄alkoxycarbonyl, C₁-C₄haloalkoxycarbonyl,aminocarbonyl, C₁-C₄alkylaminocarbonyl, bis(C₁-C₄alkylamino)carbonyl,arylaminocarbonyl, arylaminothiocarbonyl, C₁-C₄haloalkylcarbonyloxy,C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxycarbonyloxy, aminocarbonyloxy,C₁-C₄alkylaminocarbonyloxy, bis(C₁-C₄alkylamino)carbonyloxy,arylaminocarbonyloxy, arylaminothiocarbonyloxy, C₁-C₄alkoximinomethyl,—CSNH₂, —SH, C₁-C₄-alkylthiomethyl, C₂-C₄alkenyloxy, C₂-C₄alkynyloxy,C₂-C₄haloalkenyloxy, C₁-C₄alkylsulfinylmethyl, C₁-C₄alkylsulfonylmethyl,phenylsulfinylmethyl, phenylsulfonylmethyl, trifluoromethylsulfonyl,C₃-C₆cycloalkyl, phenyl, benzyl, phenoxy, phenylthio, benzyloxy andbenzylthio;

it being possible for the aromatic groups to carry a maximum of fivefurther substituents selected from halogen, C₁-C₄alkyl, C₁-C₄alkoxy,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, CN and NO₂, and it being possible fortwo adjacent substituents of the maximum of 5 substituents to form analiphatic bridge having a maximum of 5 members, which bridge containsfrom 0 to 2 oxygen atoms and 0 or 1 carbonyl group and may besubstituted a maximum of four times by halogen, C₁-C₄alkyl, C₁-C₄alkoxyand/or by a single phenyl group; or wherein

R₁₂ is a group e)

wherein:

R₁₃ is hydrogen, cyano, C₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆alkoxycarbonyl, heteroaryl, heterocyclyl, naphthyl, C₁-C₆alkoxy,aryloxy, heteroaryloxy, C₁-C₆alkylamino, bis(C₁-C₆-alkyl)amino,arylamino or heteroarylamino, it being possible for all of the radicalsmentioned (with the exception of cyano) to be unsubstituted orsubstituted by alkyl, alkoxy, haloalkyl, haloalkoxy, alkylthio,alkylsulfenyl, alkylsulfinyl, halogen, nitro, cyano, aryl, aryloxy,heteroaryl or by heteroaryloxy,

or a group f)

wherein

R₁₅ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy, halo-C₁-C₆alkoxy,halogen, C₃-C₆cycloalkyl unsubstituted or substituted by from 1 to 5halogen atoms, C₂-C₆alkenyl, halo-C₂-C₆alkenyl, optionally substitutedC₃-C₆alkynyl, cyano, cyano-C₁-C₂alkyl, cyano-C₁-C₂alkoxy, OH, NO₂, SCN,thiocyanomethyl, Si(CH₃)₃, NH₂, NH(C₁-C₄alkyl), N(C₁-C₄alkyl)₂,C₁-C₄alkoxymethyl, C₁-C₄haloalkylcarbonyl, C₁-C₄alkylcarbonyl,C₁-C₄alkoxycarbonyl, aminocarbonyl, C₁-C₄alkylaminocarbonyl,bis(C₁-C₄alkylamino)carbonyl, arylaminocarbonyl, arylaminothiocarbonyl,C₁-C₄alkoximinomethyl, —CSNH₂, —SH, C₁-C₄alkylthiomethyl,C₂-C₄alkenyloxy, C₂-C₄alkynyloxy, C₂-C₄haloalkenyloxy,C₁-C₄alkylsulfinylmethyl, C₁-C₄alkylsulfonylmethyl,phenylsulfinylmethyl, phenylsulfonylmethyl, trifluoromethylsulfonyl,C₃-C₆cycloalkyl, C₁-C₄haloalkylcarbonyloxy, C₁-C₄alkylcarbonyloxy,C₁-C₄alkoxycarbonyloxy, aminocarbonyloxy, C₁-C₄alkylaminocarbonyloxy,bis(C₁-C₄alkylamino)carbonyloxy, arylaminocarbonyloxy,arylaminothiocarbonyloxy, aryl, heteroaryl or heterocyclyl; the aromaticgroups in R₁₅ each independently of the others being unsubstituted ormono- to penta-substituted by C₁-C₆alkyl, halo-C₁-C₆alkyl, halogen,C₁-C₆alkoxy or by halo-C₁-C₆alkoxy; tri(C₁-C₄alkyl)silyl ordi(C₁-C₄alkyl)phenylsilyl;

wherein when n is greater than 1 the R₁₅ radicals may be identical ordifferent;

Q is a direct bond, C₁-C₈alkylene, C₂-C₆alkenylene, C₂-C₆alkynylene, O,O(C₁-C₆alkylene), (C₁-C₆alkylene)O, S(═O)_(p), S(═O)_(p)(C₁-C₆alkylene)or (C₁-C₆alkylene)S(═O)_(p);

m is 0, 1, 2, 3, 4 or 5;

p is 0, 1 or 2; and

R₁₄ is hydrogen; C₁-C₆alkyl; C₁-C₆haloalkyl having from 1 to 15 halogenatoms; C₁-C₄-alkoxy-C₁-C₂alkyl; C₂-C₄alkenyl-C₁-C₂alkyl unsubstituted orsubstituted by from 1 to 3 halogen atoms; C₂-C₄alkynyl-C₁-C₂alkyl;C₃-C₆cycloalkyl unsubstituted or substituted by from 1 to 4 halogenatoms; C₃-C₆cycloalkyl-C₁-C₄alkyl unsubstituted or substituted by from 1to 4 halogen atoms; cyano-C₁-C₄alkyl; C₁-C₄alkoxycarbonyl-C₁-C₄alkyl;phenyl-C₁-C₃alkyl unsubstituted or substituted by halogen, C₁-C₃alkyl,C₁-C₄alkoxy, C₁-C₄haloalkyl, cyano, nitro and/or by C₁-C₄alkylenedioxyand wherein the phenyl group may be substituted by from 1 to 3 identicalor different substituents; phenyl unsubstituted or substituted by one ortwo substituents, which may be the same or different, selected fromC₁-C₄alkyl, C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3halogen atoms, nitro and cyano; or pyridyl unsubstituted or substitutedby one or two substituents, which may be the same or different, selectedfrom C₁-C₄alkyl, C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3halogen atoms, nitro and cyano.

(2) Compounds of formula I wherein:

R₁ is methyl;

R₂, R₃ and R₅ are each independently of the others C₁-C₂alkyl,preferably methyl; and

R₄ is hydrogen.

(3) Compounds of formula I wherein:

X is N;

Y is O, S or S═O preferably O;

Z is OR₂, SR₂ or N(R₃)H; preferably OR₂ or SR₂; and

R₂ and R₃ are C₁-C₂alkyl, preferably methyl.

(4) Compounds of formula I wherein:

X is CH;

Y is O, S or S═O, preferably O;

Z is OR₂; and

R₂ is C₁-C₂alkyl, preferably methyl.

(5) Compounds of formula I wherein Y and Z together are a group

wherein:

A is unsubstituted or methyl-substituted alkanediyl having from 1 to 3carbon atoms, preferably dimethylene (ethane-1,2-diyl); and

R₆ is hydrogen, C₁-C₃alkyl, cyclopropyl or CF₃;

(6) Compounds of formula I wherein:

R₈ and R₉ are hydrogen or methyl;

R₂₁ and R₂₂ are each independently of the other hydrogen, chlorine,bromine, C₁-C₄alkyl or C₁-C₄alkoxy;

R₂₃, R₂₄, R₂₅ and R₂₆ are hydrogen; and

n is 0, 1 or 2.

(7) Compounds of formula I wherein:

R₈ and R₉ are hydrogen;

R₂₁ and R₂₂ are each independently of the other hydrogen or methyl; and

n is 0.

(8) Compounds of formula I in which in group a)

R₁₁ is hydrogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, cyclopropyl,C₁-C₄alkoxymethyl, C₁-C₄alkoxy, C₁-C₄alkylthio or cyano; and

R₁₂ is phenyl or pyridyl each unsubstituted or substituted.

(9) Compounds of formula I in which in group a)

R₁₁ is C₁-C₄alkyl, cyclopropyl, or cyano; and

R₁₂ is phenyl unsubstituted or substituted by one or two substituents,which may be the same or different, selected from C₁-C₄alkyl,C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3 halogen atoms,C₂-C₄alkenyl, C₂-C₄alkynyl, nitro and cyano; or pyridyl unsubstituted orsubstituted by one or two substituents, which may be the same ordifferent, selected from C₁-C₄alkyl, C₁-C₄alkoxy, halogen,C₁-C₂haloalkyl having from 1 to 3 halogen atoms, nitro and cyano.

(10) Compounds of formula I in which in group a)

R₁₁ is hydrogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, cyclopropyl,C₁-C₄alkoxymethyl, C₁-C₄alkoxy, C₁-C₄alkylthio or cyano; and

R₁₂ is a group e)

(11) Compounds of formula I in which in group e)

R₁₃ is hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, cyano or a group f)

wherein

R₁₅ is C₁-C₆alkyl, halo-C₁-C₆alkyl, cyclopropyl unsubstituted orsubstituted by from 1 to 5 chlorine atoms, C₂-C₆alkenyl unsubstituted orsubstituted by from 1 to 3 halogen atoms, or unsubstituted orsubstituted C₃-C₆alkynyl; also phenyl unsubstituted or mono- topenta-substituted by C₁-C₆alkyl, halo-C₁-C₆alkyl, halogen, C₁-C₆alkoxyor by halo-C₁-C₆alkoxy; or pyridyl unsubstituted or mono- totetra-substituted by C₁-C₆alkyl, halo-C₁-C₆alkyl, halogen, C₁-C₆alkoxyor by halo-C₁-C₆alkoxy;

Q is a direct bond, C₁-C₄alkylene, O, O(C₁-C₄alkylene) or(C₁-C₄alkylene)O,

m is 0, 1 or 2; and

R₁₄ is hydrogen; C₁-C₆alkyl; C₁-C₆haloalkyl having from 1 to 15 halogenatoms; C₁-C₄-alkoxy-C₁-C₂alkyl; C₂-C₄alkenyl-C₁-C₂alkyl unsubstituted orsubstituted by from 1 to 3 halogen atoms; C₂-C₄alkynyl-C₁-C₂alkyl;C₃-C₆-cycloalkyl unsubstituted or substituted by from 1 to 4 halogenatoms; C₃-C₆cycloalkyl-C₁-C₄alkyl unsubstituted or substituted by from 1to 4 halogen atoms; cyano-C₁-C₄alkyl; C₁-C₄alkoxycarbonyl-C₁-C₄alkyl;phenyl-C₁-C₃alkyl unsubstituted or substituted by halogen, C₁-C₃alkyl,C₁-C4alkoxy, C₁-C₄haloalkyl, cyano, nitro and/or by C₁-C₄alkylenedioxywherein the phenyl group may be substituted by from 1 to 3 identical ordifferent substituents; phenyl unsubstituted or substituted by one ortwo substituents, which may be the same or different, selected fromC₁-C₄alkyl, C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3halogen atoms, nitro and cyano; or pyridyl unsubstituted or substitutedby one or two substituents, which may be the same or different, selectedfrom C₁-C₄alkyl, C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3halogen atoms, nitro and cyano.

(12) Compounds of formula I in which in group a)

R₁₁ is methyl;

R₁₂ is a group e)

R₁₃ is a group f)

wherein

R₁₅ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy, halo-C₁-C₆alkoxy,halogen, C₃-C₆-cycloalkyl unsubstituted or substituted by from 1 to 5halogen atoms, C₂-C₆alkenyl, halo-C₂-C₆alkenyl, C₃-C₆alkynyl, cyano,cyano-C₁-C₂alkyl, cyano-C₁-C₂alkoxy, OH, NO₂, SCN, thiocyanomethyl,Si(CH₃)₃, NH₂, NH(C₁-C₄alkyl), N(C₁-C₄alkyl)₂, C₁-C₄alkoxymethyl,C₁-C₄haloalkylcarbonyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl,aminocarbonyl, C₁-C₄alkylaminocarbonyl, bis(C₁-C₄alkylamino)carbonyl,arylaminocarbonyl, arylaminothiocarbonyl, C₁-C₄alkoximinomethyl, —CSNH₂,—SH, C₁-C₄alkylthiomethyl, C₂-C₄alkenyloxy, C₂-C₄alkynyloxy,C₂-C₄halo-alkenyloxy, C₁-C₄alkylsulfinylmethyl,C₁-C₄alkylsulfonylmethyl, phenylsulfinylmethyl, phenylsulfonylmethyl,trifluoromethylsulfonyl, C₃-C₆cycloalkyl, C₁-C₄haloalkylcarbonyloxy,C₁-C₄-alkylcarbonyloxy, C₁-C₄alkoxycarbonyloxy, aminocarbonyloxy,C₁-C₄alkylaminocarbonyloxy, bis(C₁-C₄alkylamino)carbonyloxy,arylaminocarbonyloxy, arylaminothiocarbonyloxy, aryl, heteroaryl orheterocyclyl; wherein the aromatic groups in R₁₅ are each independentlyof the other unsubstituted or mono- to penta-substituted by C₁-C₆alkyl,halo-C₁-C₆alkyl, halogen, C₁-C₆alkoxy or by halo-C₁-C₆alkoxy;

Q is a direct bond, C₁-C₄alkylene, C₂-C₄alkenylene, C₂-C₄alkynylene, O,O(C₁-C₂alkylene) or (C₁-C₂alkylene)O;

m is 0 or 1; and

R₁₄ is methyl, ethyl or propargyl.

(13) Compounds of formula I in which in group e)

R₁₃ is heteroaryl or heterocyclyl, which are each independently of theother unsubstituted or mono- to penta-substituted by C₁-C₆alkyl,halo-C₁-C₆alkyl, halogen, C₁-C₆alkoxy or by halo-C₁-C₆alkoxy.

(14) Compounds of formula I wherein in group e)

R₁₃ is pyridyl, pyrimidinyl, imidazolyl, thiazolyl or pyrrolyl eachunsubstituted or mono- to tri-substituted by methyl, halo-C₁-C₂alkyl,C₁-C₂alkoxy, halo-C₁-C₂alkoxy or by halogen.

Compounds of formula I may be prepared as follows in accordance withReaction Schemes 1 and 2.

In detail the reaction steps may be carried out as follows:

A), E), F) Under conditions that are known and can be used forDiels-Alder reactions, in the presence or absence of solvents, in thepresence or absence of a catalyst, at from −40° to 250° C., preferablyat from 20° to 200° C.

B), G) Reaction in a solvent under basic conditions.

C), K) Reaction with a chloroformic acid ester in the presence orabsence of solvents, in the absence of water.

D), H), J) Under conditions that are known and can be used for Heckreactions in the presence of a palladium catalyst.

M) Replacement of the leaving group by an amino group under basicconditions.

N) Reaction with a chloroformic acid ester in the presence or absence ofsolvents, in the absence of water, to form a compound of formula VIIIwherein L is chlorine, then, if desired, replacement of the chlorineatom by a different leaving group, such as bromine, tosylate ormesylate.

O) 1) Metallation with appropriate reagents, such as, for example,methylmagnesium chloride, sodium hydride, alkyllithium or potassiumtert-butanolate and, if desired, transmetallation with copper iodide orsimilar salts and 2) subsequent acylation of the metal acetylide with anoxalic acid derivative T—Cl, especially with T1—Cl or T₁—O(C₁-C₆alkyl)in a solvent.

Q) Wittig reaction with, for example, methoxymethyltriphenylphosphoniumchloride and base in an inert solvent.

R) Oxime formation either (a) with a hydroxylamine derivative of formulaH₂NOR₁ in a neutral or basic solvent, if desired with the addition of abase, or (b) with hydroxylamine H₂NOH or a salt thereof and subsequentalkylation with an alkylation agent R₁-L in which L is a leaving group.

S) Conversion of an ester into an amide by treatment of the ester withan amine HNR₃R₄ in a suitable solvent.

Suitable bases are, for example, alkali metal or alkaline earth metalhydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides oralkylsilylamides, alkylamines, alkylenediamines, unsubstituted orN-alkylated, saturated or unsaturated cycloalkylamines, basicheterocycles, ammonium hydroxides and also carbocyclic amines. There maybe mentioned by way of example sodium hydroxide, hydride, amide,methanolate and carbonate, potassium tert-butanolate and carbonate,lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calciumhydride, triethylamine, triethylenediamine, cyclohexylamine,bis(trimethylsilyl)amide, calcium hydride, triethylamine,triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine,N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)-pyridine,N-methylmorpholine, benzyltrimethylammonium hydroxide and also1,8-diazabicyclo[5.4.0]undec-5-ene (DBU).

Leaving groups are, for example, chlorine, bromine, iodine,C₁-C₈alkylthio, such as methylthio, ethylthio or propylthio,C₁-C₈alkanoyloxy, such as acetoxy, (halo-)C₁-C₈alkanesulfonyloxy, suchas methanesulfonyloxy, ethanesulfonyloxy or trifluoromethanesulfonyloxy,or unsubstituted or substituted phenylsulfonyloxy, such asbenzenesulfonyloxy or p-toluenesulfonyloxy, imidazolyl or hydroxy,preferably chlorine, bromine, iodine, trifluoromethanesultonyloxy orp-toluenesulfonyloxy.

The reactants may be reacted with one another as they are, that is tosay without the addition of a solvent or diluent, for example in themelt. Generally, however, the addition of an inert solvent or diluent ora mixture thereof is advantageous. Examples of such solvents or diluentsinclude: aromatic, aliphatic and alicyclic hydrocarbons and halogenatedhydrocarbons, such as benzene, toluene, xylene, chlorobenzene,bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,trichloromethane, dichloroethane and trichloroethane; ethers, such asdiethyl ether, tert-butyl methyl ether, tetrahydrofuran and dioxane;ketones, such as acetone and methyl ethyl ketone; alcohols, such asmethanol, ethanol, propanol, butanol, ethylene glycol and glycerol;esters, such as ethyl acetate and butyl acetate; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone andhexamethylphosphoric acid triamide; nitriles, such as acetonitrile; andsulfoxides, such as dimethyl sulfoxide. Bases used in excess, such astriethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, mayalso serve as solvents or diluents,.

The reaction may also be carried out with phase transfer catalysis in anorganic solvent, for example methylene chloride or toluene, in thepresence of an aqueous basic solution, for example sodium hydroxidesolution, and of a phase transfer catalyst, for exampletetrabutylammonium hydrogen sulfate.

Typical reaction conditions will be found in the Examples.

The invention relates also to novel starting materials and intermediatesused in the preparation of compounds of formula 1, to the use thereofand to processes for the preparation thereof.

In that connection the following processes are especially important:

(1) A process for the preparation of a compound of formula I whichcomprises reacting a compound of formula II with a compound of formulaIII

 wherein n, X, Y, Z, R₁, R₈, R₉, W and R₂₁ to R₂₆ are as defined forformula I.

(2) A process for the preparation of a compound of formula I whichcomprises reacting a compound of formula IV with a compound of formula V

 wherein n, X, Y, Z, R₁, R₈, R₉, R₂₁ to R₂₆ and W are as defined forformula I and L is a leaving group, in a solvent under basic conditions.

(3) A process for the preparation of a compound of formula XIV whichcomprises reacting a compound of formula II with a compound of formulaXIII

 wherein n, Y, Z, R₈, R₉, W and R₂₁ to R₂₆ are as defined for formula Iaccording to claim 1.

The following intermediates are of particular importance:

(1) Compounds of formula IV

 wherein n, X, Y, Z, R₁, R₈, R₉ and R₂₁ to R₂₆ are as defined forformula I and L is a leaving group.

(2) Compounds of formula XII

 wherein n, X, Y, Z, R₁, R₈, R₉ and R₂₁ to R26 are as defined forformula I and wherein R₃₁ and R₃₂ are each independently of the otherC₁-C₆alkyl, C₁-C₆alkenyl, C₁-C₆alkoxyalkyl, C₃-C₆cycloalkyl orunsubstituted or substituted benzyl, or R₃₁ and R₃₂ together with thenitrogen atom are an unsubstituted or substituted 6- or 7-membered ringthat may contain a further hetero atom O, S or N in addition to thenitrogen atom,

(3) Compounds of formula XIV

 wherein n, Y, Z, W, R₈, R₉ and R₂₁ to R₂₆ are as defined for formula Iaccording to claim 1.

(4) Compounds of formula III

 wherein n, X, Y, Z, W, R₁, R₈ and R₉ are as defined for formula Iaccording to claim 1.

(5) Compounds of formula XIII

 wherein n, Y, Z, W, R₁, R₈ and R₉ are as defined for formula Iaccording to claim 1.

(6) Compounds of formula XV

 wherein n, R₈, R₉, R₁₁, R₁₃ and R₁₄ are as defined for formula Iaccording to claim 1, with the exception of the following compound:

 which is known from Tetrahedron Letters 1980, pages 1445-7.

The compounds of formula T-Hal (VII) wherein T is as definedhereinbefore and Hal is halogen may be prepared as described, forexample, in WO/20569. The groups mentioned for X, Y and Z in formula Imay also be converted one into another according to known methods, forexample as described in WO 94/26700 and WO 95/04728, both in the finalstep and at any suitable intermediate step.

The compounds of formula I may be used preventatively and/or curativelyin the agricultural sector and related fields as active ingredients inthe control of plant pests. The compounds of formula I according to theinvention are distinguished by excellent activity even at low rates ofconcentration, are well tolerated by plants and are environmentallyfriendly. They possess very advantageous, especially systemic,properties and can be used for the protection of a large number of cropplants. With the compounds of formula I it is possible to inhibit ordestroy the pests that occur on plants or parts of plants (the fruit,blossom, leaves, stems, tubers or roots) of various crops of usefulplants, while the parts of plants that grow later are also protected,for example, against phytopathogenic microorganisms.

The compounds I can also be used as dressings in the treatment of seed(fruit, tubers, grains) and plant cuttings to provide protection againstfungus infections as well as against phytopathogenic fungi which occurin the soil.

The compounds I are effective, for example, against phytopathogenicfungi belonging to the following classes: Fungi imperfecti (e.g.Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercosporaand Altemaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia,Puccinia). They are furthermore effective against the classes of theAscomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia,Uncinula) and of the Oomycetes (e.g. Phytophthora, Pythium, Plasmopara).

Within the scope of the invention, target crops for plant protection useinclude e.g. the following species of plants: cereals (wheat, barley,rye, oats, rice, maize, sorghum and related crops); beet (sugar beet andfodder beet); pomes, stone fruit and soft fruit (apples, pears, plums,peaches, almonds, cherries, strawberries, raspberries and blackberries);leguminous plants (beans, lentils, peas, soybeans); oil plants (rape,mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoabeans, groundnuts); cucumber plants (marrows, cucumber, melons); fibreplants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons,grapefruit, mandarins); vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae(avocados, cinnamon, camphor); and plants such as tobacco, nuts, coffee,aubergines, sugar cane, tea, pepper, vines, hops, bananas and naturalrubber plants, as well as ornamentals.

The compounds of formula I according to the invention, while being welltolerated by warm-blooded animals, fish and plants, are valuable activeingredients against insects and pests of the order Acarina as occur inuseful plants and ornamentals in agriculture, horticulture and forestry.The compounds of formula I are suitable especially in the control ofpests in cotton, vegetable, fruit and rice crops, such as spider mites,aphids, Lepidoptera caterpillars and rice cicadas. Mainly they can beused to control spider mites such as Panonychus ulmi, aphids such asAphis craccivora, Lepidoptera caterpillars such as those of Heliothisvirescens, and rice cicadas such as Nilaparvata lugens or Nephotettixcincticeps. The good pesticidal action of the compounds I according tothe invention corresponds to a mortality rate of at least 50-60% of thementioned pests.

Further areas of use of the compounds according to the invention are:protection of stored goods and materials, where the stored goods areprotected against rotting and becoming mouldy and also against animalpests (e.g. grain weevils, mites, fly maggots etc.). In the hygienesector, compounds of formula I are effective in the control of animalparasites, such as ticks, mites, botiflies etc., on domestic animals andproductive livestock. The compounds I are effective against individualor all development stages of normally sensitive, but also resistant,species of pests. Their activity may manifest itself, for example, inthe death of the pests, which occurs directly or happens only after sometime, for example during shedding, or in a reduced oviposition and/orhatching rate.

The compounds I are usually used in the form of compositions and may beapplied to the area or plant to be treated simultaneously with or insuccession with other active ingredients. Those other active ingredientsmay be, for example, fertilisers, micronutrient donors or otherpreparations that influence plant growth. It is also possible to useselective herbicides and also insecticides, fungicides, bactericides,nematicides or molluscicides or mixtures of several of thosepreparations, where appropriate together with further carriers,surfactants or other application-promoting additives that are customaryin formulation technology.

Suitable carriers and additives may be solid or liquid and aresubstances that are expedient in formulation technology, for examplenatural or regenerated mineral substances, solvents, dispersing agents,wetting agents, tackifiers, thickening agents, binders or fertilisers.

A preferred method of applying a compound of formula I or anagrochemical composition that comprises at least one of those compoundsis foliar application. The frequency and rate of application depend onthe risk of infestation by the pathogen in question. The compounds I mayalso penetrate the plants through the root system via the soil (systemicaction) as a result of impregnation of the locus of the plant with aliquid preparation or by means of introduction of the compounds into thesoil in solid form, for example in the form of granules (soilapplication). In the case of paddy rice crops, such granules may beapplied in metered amounts to the flooded rice field. The compounds Imay, however, for seed treatment, alternatively be applied to the seedgrains (coating), either by means of impregnating the seeds or tuberswith a liquid preparation of the active ingredient or coating them witha solid preparation.

The compounds of formula I may be used in unmodified form or preferablytogether with the adjuvants conventionally employed in formulationtechnology. For that purpose they are advantageously formulated in knownmanner, for example into emulsifiable concentrates, coatable pastes,directly sprayable or dilutable solutions, dilute emulsions, wettablepowders, soluble powders, dusts or granules, e.g. by encapsulation insubstances, for example polymeric substances. As with the nature of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering, coating or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances.

Favourable rates of application are generally from 5 g to 2 kg of activeingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kga.i./ha, especially from 20 g to 600 g a.i./ha. When used as seeddressing, concentrations of from 10 mg to 1 g of active ingredient perkg of seed are advantageously employed.

The formulations, i.e. the compositions, preparations or mixturescomprising the compound (active ingredient) of formula I and, whereappropriate, a solid or liquid adjuvant, are prepared in known manner,e.g. by intimately mixing and/or grinding the active ingredient withextenders, such as solvents, solid carriers and, where appropriate,surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, such as xylene mixtures or substitutednaphthalenes, phthalates, such as dibutyl or dioctyl phthalate,aliphatic hydrocarbons, such as cyclohexane, or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycol,ethylene glycol monomethyl or monoethyl ether, ketones, such ascyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone,dimethyl sulfoxide or dimethylformamide, and also vegetable oils orepoxidised vegetable oils, such as epoxidised coconut oil or soybeanoil, and water.

The solid carriers used e.g. for dusts and dispersible powders arenormally natural mineral fillers, such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable non-sorbent carriers are, for example,calcite or sand. In addition, a great number of pregranulated materialsof inorganic or organic nature can be used, such as dolomite orpulverised plant residues.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are non-ionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term “surfactants” will also be understood as comprising mixtures ofsurfactants.

Both so-called water-soluble soaps and water-soluble syntheticsurface-active compounds are suitable anionic surfactants.

Examples of non-ionic surfactants are nonylphenol polyethoxyethanols,castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts,tributylphenoxypolyethylene ethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol. Fatty acids esters ofpolyoxyethylenesorbitan, e.g. polyoxyethylene sorbitan trioleate, arealso suitable.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈-C₂₂alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals.

Other surfactants customarily used in formulation technology are knownto the person skilled in the art or can be found in the relevantspecialised literature.

The agrochemical compositions usually contain 0.1 to 99% by weight,especially 0.1 to 95% by weight, of a compound of formula I, 99.9 to 1%by weight, especially 99.8 to 5% by weight, of a solid or liquidadjuvant, and 0 to 25% by weight, especially 0.1 to 25% by weight, of asurfactant.

Whereas commercial products are preferably formulated as concentrates,the end user will normally employ dilute formulations.

The compositions may also comprise further ingredients, such asstabilisers, anti-foams, viscosity regulators, binders or tackifiers, aswell as fertilisers or other active ingredients for obtaining specialeffects.

PREPARATION EXAMPLES Temperatures are Indicated in ° Celsius

P-1: Preparation of (3-trifluoromethylphenyl)ethanone O-prop-2-ynyloxime(Compd. 9.06)

350 g of potassium carbonate (powder) are added to a solution of 256 gof 1-(3-trifluoromethylphenyl)ethanone oxime in 2 litres ofacetonitrile. 100 ml of propargyl chloride are then added and themixture is stirred for 14 hours at 70°. After filtering off with suctionover Celite, the filtrate is concentrated by evaporation to yield 301 gof the title compound in the form of a light-brown oil.

P-2: Preparation of2-methoxyimino-5-[1-(3-trifluoromethylphenyl)ethylideneaminoxy]pent-3-ynoicacid methyl ester (Compd. 7.06.)

67.5 g of 1-(3-trifluoromethylphenyl)ethanone O-prop-2-ynyloxime andalso 0.3 g of copper(I) iodide and 1 g of Pd(TPP)₂Cl₂ are added to asolution of 39.5 g of 2-methoxyiminooxalic acid monochloride monomethylester in 1000 ml of triethylamine and 80 ml of THF. The mixture is thenstirred for 14 hours at 80° and subsequently filtered with suction andconcentrated by evaporation. The oily residue is chromatographed onsilica gel (ether/hexane 1:2) and the combined fractions areconcentrated by evaporation and stirred with hexane. 38 g of the titlecompound are obtained in the form of light-yellow crystals having amelting point of 66-68°.

P-3: Preparation of{4,5-dimethyl-2-[1-(3-trifluoromethylphenyl)ethylideneaminoxymethyl]-cyclohexa-1,4-dienyl}methoxyiminoaceticacid methyl ester (Compd. 2.05.)

7.5 ml of 2,3-dimethylbuta-1,3-diene are added to a solution of 2.5 g of2-methoxyimino-5-[1-(3-trifluoromethylphenyl)ethylideneaminoxy]pent-3-ynoicacid methyl ester in 5 ml of toluene. The reaction mixture is heated for14 hours at 130° in an autoclave and is then concentrated by evaporationand chromatographed on silica gel. 2.6 g of the title compound areobtained in the form of a resin.

P-4: Preparation of1-[4-(3-trifluoromethylphenoxy)phenyl]propane-1,2-dione1-(O-methyloxime) 2-(O-prop-2-ynyloxime) (Compd. 9.21.)

4.7 g of propargyl mesylate and 4.5 g of potassium carbonate are addedto a solution of 6 g of1-[4-(3-trifluoromethylphenoxy)phenyl]propane-1,2-dione1-(O-methyloxime) 2-oxime in 100 ml of dimethylformamide. The mixture isstirred for 6 hours at 60° and then filtered over Celite andconcentrated by evaporation under a high vacuum. 200 ml of water areadded to the residue and extraction is carried out 3 times with 50 ml ofether each time. The extracts are then concentrated by evaporation andthe residue is chromatographed on silica gel (ether/hexane 2:5). 4.9 gof the title compound are obtained in the form of a light-coloured oil.

P-5: Preparation of1-[4-(3-trifluoromethylbenzyloxy)phenyl]propane-1,2-dione1-(O-methyloxime) 2-(O-prop-2-ynyloxime) (Compd. 9.15.)

4.2 g of propargyl mesylate and 4.5 g of potassium carbonate are addedto a solution of 5.6 g of1-[4-(3-trifluoromethylbenzyloxy)phenyl]propane-1,2-dione1-(O-methyloxime) 2-oxime in 100 ml of dimethylformamide. The mixture isstirred for 6 hours at 60° and then filtered over Celite andconcentrated by evaporation under a high vacuum. 200 ml of water areadded to the residue and extraction is carried out 3 times with 50 ml ofether each time. The extracts are then concentrated by evaporation andthe residue is chromatographed on silica gel (ether/hexane 2:5). 4.9 gof the title compound are obtained in the form of a light-coloured oil.

P-6: Preparation of5-(2,6-dimethylmorpholin-4-yl)-2-methoxyiminopent-3-ynoic acid methylester (cis and trans) (Compd. 8.14.)

9 g of 2-methoxyimino-oxalic acid monochloride monomethyl ester and also0.1 g of copper(I) iodide and 0.3 g of Pd(TPP)₂Cl₂ are added to asolution of 7.65 g of 2,6-dimethyl-4-prop-2-ynylmorpholine (cis/transmixture) in 200 ml of triethylamine and 50 ml of THF. The mixture isthen stirred for 14 hours at 80° and subsequently filtered with suctionand concentrated by evaporation. The oily residue is chromatographed onsilica gel (ether/hexane 1:2). 2.1 g of oil of the (trans) titlecompound and 4.2 g of oil of the (cis) title compound are obtained.

P-7: Preparation of[2-(2,6-dimethylmorpholin-4-ylmethyl)-4,5-dimethylcyclohexa-1,4-dienyl]-methoxyiminoaceticacid methyl ester (Compd.5.11.)

7.5 ml of 2,3-dimethylbuta-1,3-diene are added to a solution of 3.3 g of(cis)-5-(2,6-dimethylmorpholin-4-yl)-2-methoxyiminopent-3-ynoic acidmethyl ester in 5 ml of toluene. The reaction mixture is heated for 14hours at 130° in an autoclave, and is then concentrated by evaporationand chromatographed on silica gel. 2.6 g of the title compound areobtained in the form of a resin.

P-8: Preparation of 2-methoxyimino-5-morpholin-4-ylpent-3-ynoic acidmethyl ester (Compd. 8.06.)

7.6 g of 2-methoxyimino-oxalic acid monochloride monomethyl ester andalso 0.1 g of copper(I) iodide and 0.3 g of Pd(TPP)₂Cl₂ are added to asolution of 6.25 g of 4-prop-2-ynylmorpholine in 250 ml of triethylamineand 30 ml of THF. The mixture is then stirred for 14 hours at 80° andsubsequently filtered with suction and concentrated by evaporation. Theoily residue is chromatographed on silica gel (ethyl acetate/hexane4:1). 6.65 g of oil of the title compound are obtained.

P-9: Preparation of(4,5-dimethyl-2-morpholin-4-ylmethylcyclohexa-1,4-dienyl)-methoxyiminoaceticacid methyl ester (Compd. 5.07)

10 ml of 2,3-dimethylbuta-1,3-diene are added to a solution of 4.8 g of2-methoxyimino-5-morpholin-4-ylpent-3-ynoic acid methyl ester in 10 mlof toluene. The reaction mixture is heated for 24 hours at 130° in anautoclave and is then concentrated by evaporation and chromatographed onsilica gel (ethyl acetate/hexane 1:2). 3 g of the title compound areobtained in the form of a resin.

P-10: Preparation of(2-chloromethyl-4,5-dimethylcyclohexa-1,4-dienyl)methoxyiminoacetic acidmethyl ester (Compd. 5.03.)

1.4 ml of chloroformic acid ethyl ester are added to a solution of 2.3 gof(4,5-dimethyl-2-morpholin-4-ylmethylcyclohexa-1,4-dienyl)methoxyiminoaceticacid methyl ester in 25 ml of THF. The mixture is then heated at 65° for20 hours and, after concentration by evaporation, chromatographed onsilica gel (ether/hexane 1:2). 1.5 g of the title compound are obtainedin the form of a colourless oil.

P-11: Preparation of{4,5-dimethyl-2-[1-(3-trifluoromethylphenyl)ethylideneaminoxymethyl]-cyclohexa-1,4-dienyl}-methoxyiminoaceticacid methyl ester (Compd. 2.05.)

2.56 g of 1-(3-trifluoromethylphenyl)ethanone oxime and 3.5 g ofpotassium carbonate (powder) are added to a solution of 2.5 g of(2-chloromethyl-4,5-dimethylcyclohexa-1,4-dienyl)methoxyiminoacetic acidmethyl ester in 5 ml of acetonitrile. The mixture is then stirred for 14hours at 70° and subsequently filtered with suction and concentrated byevaporation. Chromatography on silica gel yields 3.5 g of the titlecompound in the form of a colourless resin.

P.12: Preparation of2-{4,5-dimethyl-2-[1-(3-trifluoromethylphenyl)ethylideneaminoxymethyl]cyclohexa-1,4-dienyl}-2-methoxyimino-N-methylacetamide(Compd. 3.05.)

10 ml of methylamine solution (5N in methanol) are added to a solutionof 4 g of{4,5-dimethyl-2-[1-(3-trifluoromethylphenyl)ethylideneaminoxymethyl]cyclohexa-1,4-dienyl}-methoxyiminoaceticacid methyl ester in 10 ml of methanol and the mixture is stirred for 6hours at approximately 40° and then concentrated by evaporation andchromatographed on silica gel. 3.8 g of the title compound are obtainedin the form of a resin.

P-1 3: Preparation of 5-chloro-2-methoxyiminopent-3-ynoic acid methylester (Compd. 8.04.)

1.4 ml of chloroformic acid ethyl ester are added to a solution of 12.1g of 2-methoxyimino-5-morpholin-4-ylpent-3-ynoic acid methyl ester in 25ml of THF. The mixture is then heated for 20 hours at 65°. Concentrationby evaporation followed by chromatography on silica gel (ether/hexane1:2) yields 8.2 g of the title compound in the form of a colourless oil.

P-14: Preparation of2-methoxyimino-5-[1-(3-trifluoromethytylphenyl)ethylideneaminoxy]-pent-3-ynoicacid methyl ester (Compd. 7.06.)

10.56 g of 1-(3-trifluoromethylphenyl)ethanone oxime and 14.5 g ofpotassium carbonate (powder) are added to a solution of 10.5 g of5-chloro-2-methoxyiminopent-3-ynoic acid methyl ester in 5 ml ofacetonitrile. The mixture is then stirred for 14 hours at 70° andsubsequently filtered with suction and concentrated by evaporation.Chromatography on silica gel yields 13.5 g of the title compound in theform of a colourless resin.

P-15: Preparation ofmethoxyimino-(2-{2-methoxyimino-1-methyl-2-[4-(3-trifluoromethylbenzyloxy)phenyl]ethylideneaminoxymethyl}-4,5-dimethylcyclohexa-1,4-dienyl)aceticacid methyl ester (Compd. 3.18.)

1.56 g of 1-[4-(3-trifluoromethylbenzyloxy)phenyl]lpropane-1,2-dione1-(O-methyloxime) 2-oxime and 1.5 g of potassium carbonate (powder) areadded to a solution of 1.5 g of(2-chloromethyl-4,5-dimethylcyclohexa-1,4-dienyl)methoxyiminoacetic acidmethyl ester in 5 ml of acetonitrile. The mixture is then stirred for 14hours at 70° and subsequently filtered with suction and concentrated byevaporation. Chromatography on silica gel yields 1.5 g of the titlecompound in the form of a colourless resin.

P-16: Preparation of 5-(1-methoxy-1-methylethoxy)-2-oxopent-3-ynoic acidtert-butyl ester (Compd. 10.26.)

136 ml of a methylmagnesium chloride solution (approximately 3 molar inTHF) are added dropwise at from 15° to 20° to a solution of 50 g of3-(1-methoxy-1-methylethoxy)propyne in 200 ml of methylene chloride. Themixture is then stirred for 3 hours at room temperature. The solution soobtained is added dropwise over a period of one hour, at from −40° to−50° under nitrogen, to a solution of 131 g of oxalic acid tert-butylester ethyl ester in 100 ml of methylene chloride. The mixture is thenhydrolysed with 10% ammonium chloride solution. The organic phase isseparated off and dried over sodium sulphate. Concentration byevaporation yields 292 g of a solution that still contains methylenechloride and THF in addition to the title compound.

P-17: Preparation of2-oxo-5-[1-(3-trifluoromethylphenyl)ethylideneaminoxy]pent-3-ynoic acidtert-butyl ester (Compd.11.23.)

18 ml of a hexyllithium solution (2.5 molar in hexane) are addeddropwise at −50° to a solution of (3-trifluoromethylphenyl)ethanoneO-prop-2-ynyloxime (Compd. 9.06) in 95 ml of THF. The reaction mixtureis then stirred for 90 minutes, the temperature rising to 0°. It is thencooled to −70° and a solution of 15.85 g of oxalic acid tert-butyl esterethyl ester in 30 ml of THF is added dropwise. The mixture is stirredfor 30 minutes, in the course of which the temperature is allowed torise to −50°. The mixture is then poured into 1000 ml of ice-water,rendered slightly acidic with a small amount of hydrochloric acid andextracted three times with 200 ml of ethyl acetate each time. Theorganic phase is washed twice with brine and dried with sodium sulfate.Concentration by evaporation yields 21.9 g of a light-brown liquid whichcontains approximately 14 g of the title compound.

P-18: Preparation of{4-methyl-2-[1-(3-trifluoromethylphenyl)ethylideneaminoxymethyl]-cyclohexa-1,4-dienylloxoaceticacid tert-butyl ester (Compd. 12.171.)

19 g of isoprene are added to 14.6 g of2-oxo-5-[1-(3-trifluoromethylphenyl)ethylideneaminoxy]pent-3-ynoic acidtert-butyl ester and the reaction mixture is then left to stand for 5days at room temperature. Concentration by evaporation yields 15.38 g ofthe title compound in the form of a colourless oil.

P-19: Preparation of Compound 14.102.

2.2 g of morpholine and 1.3 g of formaldehyde as well as 0.05 g ofcopper(I) chloride are added to a solution of 5.5 g of the startingmaterial in 40 ml of 1-propanol. The mixture is heated for 3 hours at70°, concentrated by evaporation and then chromatographed on silica gel(ethyl acetate). After stirring with hexane, 4.9 g of product having amelting point of 100-102° are obtained.

H-20: Preparation of Compound 14.103.

100 mg of Pd/C (5%) are added to a solution of 0.5 g of the startingmaterial in 12 ml of tetrahydrofuran. The mixture is then hydrogenateduntil the theoretical amount of hydrogen has been consumed, and filteredwith suction, concentrated by evaporation and chromatographed on silicagel (ethyl acetate). 0.45 g of product is obtained in the form of aresin.

P-21: Preparation of Compound 14.104.

5 ml of chloroformic acid ethyl ester are added to a solution of 4.9 gof the starting material in 30 ml of tetrahydrofuran and the mixture isstirred for 14 hours at 60°. After concentration by evaporation, 150 mlof ether are added and the mixture is washed twice with sodium hydrogencarbonate solution. The organic phase is dried with magnesium sulfate,filtered with suction and concentrated by evaporation. After theconcentration by evaporation, chromatography on silica gel (ethylacetate/hexane 1:1) yields 2.1 g of product in the form of whitecrystals having a melting point of 126-129°.

P-22: Preparation of Compound 14.106.

0.19 g of 2,4-dichlorophenol and 0.19 g of potassium carbonate are addedto a solution of 0.46 g of the starting material in 2.5 ml of dimethylsulfoxide and the mixture is stirred for 3 hours at 70°. After cooling,the reaction mixture is chromatographed on silica gel (ether/hexane 1:1)to yield 0.4 g of product in the form of colourless crystals having amelting point of 119-122°.

P-23: Preparation of Compound 3.190.

15 ml of 2,3-dimethylbutadiene are added to a solution of 5 g of thestarting material in 5 ml of toluene. The mixture is then heated for 20hours at 125° in a pressure tube. After cooling, the mixture is pouredinto 150 ml of methanol and then filtered over Celite. Concentration byevaporation followed by chromatography on silica gel (ether/hexane 1:1)yields 1.6 g of product.

P-24: Preparation of Compound 2.167.

1.5 ml of iododichlorobenzene and 0.1 g of Pd(TPP)₂Cl₂ are added to asolution of 2.25 g of the starting material in 100 ml of triethylamineand 40 ml of tetrahydrofuran. The mixture is then stirred for 3 hours at65°, filtered with suction, concentrated by evaporation andchromatographed on silica gel (ethyl acetate/hexane 1:2) to yield 2.2 gof product in the form of a colourless resin.

P-25: Preparation of Compound 2.168.

100 mg of Pd/C (5%) are added to a solution of 1.8 g of the startingmaterial in 30 ml of tetrahydrofuran. The mixture is then hydrogenateduntil the theoretical amount of hydrogen has been consumed, filteredwith suction, concentrated by evaporation and chromatographed on silicagel (ethyl acetate/hexane 1:2) to yield 1.5 g of product in the form ofan oil.

P-26: Preparation of Compound 2.175.

1.1 ml of phenyl isocyanate and 0.45 ml of nitroethane and also 5 g ofdrops of triethylamine are added to a solution of 2.1 g of the startingmaterial in 40 ml of toluene. The mixture is then heated for 5 hours at80°, filtered with suction, concentrated by evaporation andchromatographed on silica gel (ethyl acetate/hexane 1:2). After stirringwith petroleum ether, 0.6 g of product is obtained in the form of acolourless resin.

P-27: Preparation of Compound 2.180.

2 ml of triethylamine are added dropwise to a solution of 1.2 g of thestarting material and 1.8 g of the chloroxime in 50 ml of toluene. Themixture is then heated for 4 hours at 65° and subsequently filtered withsuction and concentrated by evaporation. Subsequent chromatography onsilica gel (toluene/diisopropyl ether/hexane 1:1:2) yields 0.95 g ofproduct in the form of crystals having a melting point of 121-123°.

P-28: Preparation of Compound 2.170.

2 g of potassium carbonate are added to a solution of 1.5 g of(2-chloromethyl-4,5-dimethyl-cyclohexa-1,4-dienyl)methoxyiminoaceticacid methyl ester and 2 g of the bis-oxime in 40 ml of acetonitrile andthe mixture is stirred for 6 hours at 80° and then filtered with suctionand concentrated by evaporation. Subsequent chromatography on silica gel(diisopropyl ether/hexane 1:2) yields 2.4 g of product in the form of aresinous oil.

P-29: Preparation of Compound 2.164.

1.8 g of potassium carbonate are added to a solution of 1.35 g of(2-chloromethyl-4,5-dimethylcyclohexa-1,4-dienyl)methoxyiminoacetic acidmethyl ester and 1.1 g of the bisoxime in 40 ml of acetonitrile and themixture is stirred for 6 hours at 65°, filtered with suction andconcentrated by evaporation. Subsequent chromatography on silica gel(ether/hexane 1:1) yields 1.5 g of the title compound in the form of acolourless resin.

P-30: Preparation of Compound 2.166.

0.5 g of Raney nickel is added to a solution of 1 g of the startingmaterial in 15 ml of tetrahydrofuran. The mixture is then hydrogenateduntil the theoretical amount of hydrogen has been consumed, filteredwith suction and concentrated by evaporation. Subsequent chromatographyon silica gel (ether/hexane 1:1) yields 0.7 g of product in the form ofa colourless resin.

P-31: Preparation of Compound 2.184.

0.1 g of Pd(TPP)₂Cl₂ and 0.3 ml of triethylamine are added to a solutionof 1 g of the starting material in 3 ml of methanol. The mixture is thenstirred for 6 hours at 60°, poured into 40 ml of water and extractedtwice with 20 ml of ether/THF 4:1 each time. Concentration byevaporation followed by chromatography on silica gel (ether/hexane 3:1)yields 0.5 g of product in the form of a resinous oil.

P-32:) Preparation of Compound 2.183.

0.1 g of 10% Pd/C is added to a solution of 5 g of the starting materialin 30 ml of tetrahydrofuran. The mixture is then hydrogenated until oneequivalent of hydrogen has been consumed, and is subsequently filteredwith suction, concentrated by evaporation and chromatographed on silicagel (ethyl acetate/hexane 1:2) to yield 3.5 g of product in the form ofan oil.

P-33: Preparation of Compound 2.185.

0.15 g of Pd(TPP)₂Cl₂ and also 0.6 ml of triethylamine are added to asolution of 3 g of the starting material in 3 ml of methanol. Themixture is then stirred for 6 hours at 60°, poured into 40 ml of waterand extracted twice with 20 ml of ether/THF 4:1 each time. Concentrationby evaporation followed by chromatography on silica gel (ether/hexane3:1) yields 1.5 g of product in the form of a resinous oil.

P-34: Preparation of2-methoxymethylene-5-[1-(3-trifluoromethylphenyl)ethylideneaminoxy]-pent-3-ynoicacid methyl ester (Compound 7.07.)

0.25 g of Pd(TPP)₂Cl₂ and also 0.1 g of copper(I) iodide are added,under an argon atmosphere, to a solution of 10.0 g of1-(3-trifluoromethylphenyl)ethanone O-prop-2-ynyl-oxime in 150 ml oftriethylamine and the mixture is heated to 70° C. 8.9 g of2-bromo-3-methoxyacrylic acid methyl ester in 30 ml of tetrahydrofuranare then added and the mixture is stirred at 70° C. for 14 h and thenfiltered. The filtrate is concentrated by evaporation andchromatographed on silica gel (hexane/diethyl ether 2:1) to yield 4.6 gof the product having a melting point of 57-58° C.

P-35: Preparation of2-{4,5-dimethyl-2-[1-(3-trifluoromethylphenyl)ethylideneaminoxy-methyl]cyclohexa-1,4-dienyl}-3-methoxacrylicacid methyl ester (Compound 1.05.)

10 ml of 2,3-dimethylbutadiene are added to 2.00 g of2-methoxymethylene-5-[1-(3-trifluoromethylphenyl)ethylideneaminoxy]pent-3-ynoicacid methyl ester in 5 ml of toluene and heated for 64 h at 140° C. inan autoclave. The reaction mixture is concentrated in vacuo and 25 ml ofmethanol are added. The resulting syrup is extracted with meth anol .The methanol phase is filtered and concentrated. Chromatography onsilica gel (hexane/toluene/diisopropyl ether 3:1:1) yields 145 mg ofproduct in the form of a resin.

TABLE 1 Compounds of formula

wherein the substituents of compounds 1.01 to 1.189 have the meaning ofthe corresponding compounds of table 2.

Exmples:

Ex. Nr. R₂₁ R₂₂

Phys. Data 1.01. CH₃ CH₃

1.02. CH₃ CH₃

1.05. CH₃ CH₃

resin 1.12. CH₃ CH₃

1.20. CH₃ CH₃

1.21. CH₃ CH₃

1.24. CH₃ CH₃

1.26. CH₃ CH₃

1.28. CH₃ CH₃

1.33. CH₃ CH₃

1.38. CH₃ CH₃

1.103. CH₃ CH₃

1.105. CH₃ CH₃

1.111. CH₃ CH₃

1.114. CH₃ CH₃

1.117. CH₃ CH₃

1.118. CH₃ CH₃

1.119. CH₃ CH₃

1.120. CH₃ CH₃

1.121. CH₃ CH₃

1.122. CH₃ CH₃

1.123. CH₃ CH₃

1.134. CH₃ CH₃

1.135. CH₃ CH₃

1.136. CH₃ CH₃

1.137. CH₃ CH₃

1.138. CH₃ CH₃

1.140. CH₃ CH₃

1.148. CH₃ CH₃

1.149. CH₃ CH₃

1.150. CH₃ CH₃

1.153. CH₃ CH₃

1.154. CH₃ CH₃

1.160. CH₃ CH₃

1.161. H CH₃

1.162. H H

1.163. CH₃ CH₃

1.164. CH₃ CH₃

1.165. CH₃ CH₃

1.166. CH₃ CH₃

1.167. CH₃ CH₃

1.168. CH₃ CH₃

1.169. CH₃ CH₃

1.170. CH₃ CH₃

1.171. CH₃ CH₃

1.172. CH₃ CH₃

1.173. CH₃ CH₃

1.174. CH₃ CH₃

1.175. CH₃ CH₃

1.176. CH₃ CH₃

1.177. CH₃ CH₃

1.178. CH₃ CH₃

1.179. CH₃ CH₃

1.182. CH₃ CH₃

1.183. CH₃ CH₃

1.184. CH₃ CH₃

1.185. CH₃ CH₃

1.187. CH₃ CH₃

1.189. CH₃ CH₃

TABLE 1a (as Table 1, but with n = 1) Compounds of formula

Examples

Ex. Nr. R₂₁ R₂₂

Phys. Data 1a.06. CH₃ CH₃

1a.12. CH₃ CH₃

1a.20. CH₃ CH₃

1a.40. CH₃ CH₃

1a.98. CH₃ OCH₃

TABLE 1b (as Table 1, but with n = 2)

Examples

Ex. Nr. R₂₁ R₂₂

Phys. Data 1b.06. CH₃ CH₃

1b.12. CH₃ CH₃

1b.20. CH₃ CH₃

1b.40. CH₃ CH₃

1b.98. CH₃ OCH₃

TABLE 2 (n = 0)

          Ex. Nr.           R₂₁           R₂₂

          Phys. Data 2.01. CH₃ CH₃

2.02. CH₃ CH₃

2.03. CH₃ CH₃

2.04. CH₃ CH₃

2.05. CH₃ CH₃

resin 2.06. CH₃ CH₃

2.07. CH₃ CH₃

2.08. CH₃ CH₃

2.09. CH₃ CH₃

2.10. CH₃ CH₃

2.11. CH₃ CH₃

2.12. CH₃ CH₃

2.13. CH₃ CH₃

2.14. CH₃ CH₃

2.15. CH₃ CH₃

oil 2.16. CH₃ CH₃

oil 2.17. CH₃ CH₃

2.18. CH₃ CH₃

resin 2.19. CH₃ CH₃

2.20. CH₃ CH₃

2.21. CH₃ CH₃

2.22. CH₃ CH₃

2.23. CH₃ CH₃

2.24. CH₃ CH₃

oil 2.25. CH₃ CH₃

2.26. CH₃ CH₃

2.27. CH₃ CH₃

2.28. CH₃ CH₃

2.29. CH₃ CH₃

2.30. CH₃ CH₃

2.31. CH₃ CH₃

2.32. CH₃ CH₃

2.33. CH₃ CH₃

oil 2.34. CH₃ CH₃

2.35. CH₃ CH₃

2.36. CH₃ CH₃

2.37. CH₃ CH₃

2.38. CH₃ CH₃

resin 2.39. CH₃ CH₃

2.40. CH₃ CH₃

2.41. CH₃ CH₃

2.42. CH₃ CH₃

2.43. CH₃ CH₃

2.44. CH₃ CH₃

2.45. CH₃ CH₃

2.46. CH₃ CH₃

2.47. CH₃ CH₃

2.48. CH₃ CH₃

2.49. CH₃ CH₃

2.50. CH₃ CH₃

2.51. CH₃ H

2.52. CH₃ H

2.53. CH₃ H

2.54. CH₃ H

2.55. CH₃ H

2.56. H CH₃

2.57. H CH₃

2.58. H CH₃

2.59. H CH₃

2.60. H CH₃

2.61. H H

2.62. H H

2.63. H H

2.64. H H

2.65. H H

2.66. H H

2.67. H H

2.68. H H

2.69. H H

2.70. H H

2.71. Cl H

2.72. Cl H

2.73. Cl H

2.74. Cl H

2.75. Cl H

2.76. Cl H

2.77. Cl H

2.78. Cl H

2.79. Cl H

2.80. Cl H

2.81. H Cl

2.82. H Cl

2.83. H Cl

2.84. H Cl

2.85. H Cl

2.86. H Cl

2.87. H Cl

2.88. H Cl

2.89. H Cl

2.90. H Cl

2.91. OCH₃ H

2.92. OCH₃ H

2.93. OCH₃ H

2.94. OCH₃ H

2.95. OCH₃ H

2.96. H OCH₃

2.97. H OCH₃

2.98. CH₃ OCH₃

2.99. CH₃ OCH₃

2.100. OCH₃ CH₃

2.101. OCH₃ H

2.102. CH₃ CH₃

2.103. CH₃ CH₃

2.104. CH₃ CH₃

resin 2.105. CH₃ CH₃

2.106. CH₃ CH₃

2.107. CH₃ CH₃

2.108. CH₃ CH₃

2.109. CH₃ CH₃

2.110. CH₃ CH₃

2.111. CH₃ CH₃

2.112. CH₃ CH₃

2.113. CH₃ CH₃

2.114. CH₃ CH₃

resin 2.115. CH₃ CH₃

2.116. CH₃ CH₃

2.117. CH₃ CH₃

resin 2.118. CH₃ CH₃

2.119. CH₃ CH₃

resin 2.120. CH₃ CH₃

2.121. CH₃ CH₃

2.122. CH₃ CH₃

2.123. CH₃ CH₃

Resin 2.124. CH₃ CH₃

2.125. CH₃ CH₃

2.126. CH₃ CH₃

2.127. CH₃ CH₃

2.128. CH₃ CH₃

2.129. CH₃ CH₃

2.130. CH₃ CH₃

2.131. CH₃ CH₃

2.132. CH₃ CH₃

2.133. CH₃ CH₃

2.134. CH₃ CH₃

2.135. CH₃ CH₃

2.136. CH₃ CH₃

2.137. CH₃ CH₃

oil 2.138. CH₃ CH₃

150-151° 2.139. CH₃ CH₃

2.140. CH₃ CH₃

oil 2.141. CH₃ CH₃

2.142. CH₃ CH₃

2.143a. CH₃ CH₃

2.143b. CH₃ CH₃

2.144. CH₃ CH₃

2.145. CH₃ CH₃

2.146. CH₃ CH₃

2.147. CH₃ CH₃

2.148. CH₃ CH₃

oil 2.149. CH₃ CH₃

2.150. CH₃ CH₃

2.151. CH₃ CH₃

2.152. CH₃ CH₃

2.153. CH₃ CH₃

2.154. CH₃ CH₃

2.155. CH₃ CH₃

2.156. CH₃ CH₃

2.157. CH₃ CH₃

2.158. CH₃ CH₃

2.159. CH₃ CH₃

2.160. CH₃ CH₃

2.161. H CH₃

oil 2.162. H H

oil 2.163. CH₃ CH₃

oil 2.164. CH₃ CH₃

oil 2.165. CH₃ CH₃

oil 2.166. CH₃ CH₃

oil 2.167. CH₃ CH₃

oil 2.168. CH₃ CH₃

oil 2.169. CH₃ CH₃

oil 2.170. CH₃ CH₃

oil 2.171. CH₃ CH₃

oil           Ex. Nr.           R₂₁           R₂₂

          Phys. Data 2.172. CH₃ CH₃

 78-79° 2.173. CH₃ CH₃

 82-84° 2.174. CH₃ CH₃

oil 2.175. CH₃ CH₃

oil 2.176. CH₃ CH₃

 79-81° 2.177. CH₃ CH₃

110-113° 2.178. CH₃ CH₃

resin 2.179. CH₃ CH₃

 82-84° 2.180. CH₃ CH₃

121-123° 2.181. CH₃ CH₃

 95-97° 2.182. CH₃ CH₃

resin 2.183. CH₃ CH₃

resin 2.184. CH₃ CH₃

resin 2.185. CH₃ CH₃

resin 2.186. CH₃ CH₃

resin 2.187. CH₃ CH₃

resin 2.188. CH₃ CH₃

resin 2.189. CH₃ CH₃

resin

TABLE 2a (as Table 2, but with n = 1)

Examples

Ex. Nr. R₂₁ R₂₂

Phys. Data 2a.06. CH₃ CH₃

2a.12. CH₃ CH₃

2a.20. CH₃ CH₃

2a.40. CH₃ CH₃

2a.98. CH₃ OCH₃

TABLE 2b (as Table 2, but with n = 2)

Examles:

Ex. Nr. R₂₁ R₂₂

Phys. Data 2b.06. CH₃ CH₃

2b.12. CH₃ CH₃

2b.20. CH₃ CH₃

2b.40. CH₃ CH₃

2b.98. CH₃ OCH₃

2b.169. CH₃ CH₃

oil

TABLE 3 (n = 0) Compounds of formula

wherein the substituents of compounds 3.1 to 3.189 have the meaning ofthe corresponding compounds of Table 2.

Examples

Ex. Nr. R₂₁ R₂₂

Phys. Data 3.4. CH₃ CH₃

3.5. CH₃ CH₃

111-114° 3.8. CH₃ CH₃

3.12. CH₃ CH₃

3.15. CH₃ CH₃

3.16. CH₃ CH₃

3.17. CH₃ CH₃

3.18. CH₃ CH₃

resin 3.20. CH₃ CH₃

3.23. CH₃ CH₃

3.30. CH₃ CH₃

3.31. CH₃ CH₃

3.37. CH₃ CH₃

3.38. CH₃ CH₃

146-168° 3.39. CH₃ CH₃

3.40. CH₃ CH₃

3.42. CH₃ CH₃

3.46. CH₃ CH₃

3.47. CH₃ CH₃

3.48. CH₃ CH₃

3.57. H CH₃

3.58. H CH₃

3.62. H H

3.65. H H

3.66. H H

3.70. H H

3.73. Cl H

3.74. Cl H

3.92. OCH₃ H

3.93. OCH₃ H

3.94. OCH₃ H

3.95. OCH₃ H

3.96. H OCH₃

3.97. H OCH₃

3.98. CH₃ OCH₃

3.99. CH₃ OCH₃

3.100. OCH₃ CH₃

3.101. H H

oil 3.111. CH₃ CH₃

3.112. CH₃ CH₃

3.125. CH₃ CH₃

3.131. CH₃ CH₃

3.132. CH₃ CH₃

3.133. CH₃ CH₃

3.134. CH₃ CH₃

3.136. CH₃ CH₃

3.137. CH₃ CH₃

3.149. CH₃ CH₃

3.150. CH₃ CH₃

3.161. H CH₃

resin 3.163. H H

3.179. CH₃ CH₃

resin 3.180. CH₃ CH₃

3.181. CH₃ CH₃

130-131° 3.182. CH₃ CH₃

3.183. CH₃ CH₃

3.184. CH₃ CH₃

3.185. CH₃ CH₃

3.187. CH₃ CH₃

3.189. CH₃ CH₃

TABLE 3a (as Table 3, but with n = 1)

Examples

Ex. Nr. R₂₁ R₂₂

Phys. Data 3a.06. CH₃ CH₃

3a.12. CH₃ CH₃

3a.20. CH₃ CH₃

3a.40. CH₃ CH₃

3a.98. CH₃ OCH₃

TABLE 3b (as Table 3, but with n = 2)

Examples

Ex. Nr. R₂₁ R₂₂

Phys. Data 3b.06. CH₃ CH₃

3b.12. CH₃ CH₃

3b.20. CH₃ CH₃

3b.40. CH₃ CH₃

3b.98. CH₃ OCH₃

TABLE 4 (n = 0; intermediates)

Ex. Nr. R₂₁ R₂₂

Phys. Data 4.01. CH₃ CH₃

4.02. CH₃ CH₃

4.03. CH₃ CH₃

4.04. CH₃ CH₃

4.05. CH₃ CH₃

4.06. CH₃ CH₃

4.07. CH₃ CH₃

4.08. CH₃ CH₃

4.09. CH₃ CH₃

4.10. CH₃ CH₃

4.11. CH₃ CH₃

4.12. CH₃ CH₃

4.13. CH₃ CH₃

4.14. CH₃ CH₃

4.15. CH₃ CH₃

4.16. CH₃ CH₃

4.17. CH₃ CH₃

4.18. CH₃ CH₃

4.19. CH₃ CH₃

4.20. CH₃ CH₃

4.21. CH₃ H

4.22. H CH₃

4.23. H H

4.24. Cl H

4.25. H Cl

TABLE 5 (n = 0; intermediates)

Ex. Nr. R₂₁ R₂₂

Phys. Data 5.01. CH₃ CH₃

5.02. CH₃ CH₃

5.03. CH₃ CH₃

77-79° 5.04. CH₃ CH₃

5.05. CH₃ CH₃

5.06. CH₃ CH₃

5.07. CH₃ CH₃

64-66° 5.08. CH₃ CH₃

5.09. CH₃ CH₃

5.10. CH₃ CH₃

resin 5.11. CH₃ CH₃

resin 5.12. CH₃ CH₃

5.13. CH₃ CH₃

5.14. CH₃ CH₃

5.15. CH₃ CH₃

5.16. CH₃ CH₃

5.17. CH₃ CH₃

5.18. CH₃ CH₃

5.19. CH₃ CH₃

5.20. CH₃ CH₃

5.21. CH₃ H

5.22. H CH₃

5.23. H H

5.24. Cl H

5.25. H Cl

TABLE 6 (n = 0; intermediates)

Ex. Nr. R₂₁ R₂₂

Phys. Data 6.01. CH₃ CH₃

6.02. CH₃ CH₃

6.03. CH₃ CH₃

oil 6.04. CH₃ CH₃

6.05. CH₃ CH₃

6.06. CH₃ CH₃

6.07. CH₃ CH₃

resin 6.08. CH₃ CH₃

6.09. CH₃ CH₃

6.10. CH₃ CH₃

resin 6.11. CH₃ CH₃

resin 6.12. CH₃ CH₃

6.13. CH₃ CH₃

6.14. CH₃ CH₃

6.15. CH₃ CH₃

6.16. CH₃ CH₃

6.17. CH₃ CH₃

6.18. CH₃ CH₃

6.19. CH₃ CH₃

6.20. CH₃ CH₃

6.21. CH₃ H

6.22. H CH₃

6.23. H H

6.24. Cl H

6.25. H Cl

TABLE 7 (n = 0; intermediates)

Ex. Nr R₁ X Y Z

Phys. Data 7.1. CH₃ CH O OCH₃

7.2. CH₃ CH O OCH₃

7.3. CH₃ CH O OCH₃

7.4. CH₃ N O OCH₃

7.5. CH₃ N O OCH₃

7.6. CH₃ N O OCH₃

66-68° 7.7. CH₃ CH O OCH₃

57-58° 7.8. CH₃ N O NHCH₃

7.9. CH₃ N S NHCH₃

7.10. CH₃ N S NHCH₃

7.11. CH₃ N S SCH₃

7.12. CH₃ N SO SCH₃

7.13. CH₃ N SO SCH₃

7.14. CH₃ CH O SCH₃

7.15. CH₃ CH O SCH₃

7.16. CH₃ N O OCH₃

7.17. CH₃ N O NHCH₃

7.18. CH₃ N O NHCH₃

7.19. CH₃ N S NHCH₃

7.20. CH₃ N O NHCH₃

7.21. CH₃ N S SCH₃

7.22. CH₃ N S SCH₃

7.23. CH₃ N O OCH₃

oil 7.24. CH₃ N O OCH₃

oil

TABLE 8 (n = 0; intermediates)

Ex.-Nr. R₁ X Y Z

Phys. Data 8.01. Me CH O OMe

8.02. Me CH O OMe

8.03. Me CH O OMe

8.04. Me N O OMe

oil 8.05. Me N O OMe

8.06. Me N O OMe

oil 8.07. Me CH O OMe

70-72° 8.08. Me N O NHMe

8.09. Me N O OMe

oil 8.10. Me N S NHMe

8.11. Me N S SMe

8.12. Me N SO SMe

8.13. Me N SO SMe

8.14. Me N O OMe

oil 8.15. Me CH O SMe

8.16. Me N O OMe

8.17. Me N O NHMe

8.18. Me CH O OMe

8.19. Me N S NHMe

8.20. Me N O NHMe

8.21. Me N S SMe

8.22. Me N S SMe

8.23. Me N O OMe

oil 8.24. Me CH O OMe

resin

TABLE 9 (n = 0; intermediates)

Ex. Nr

Phys. Data 9.01.

9.02.

9.03.

9.04.

9.05.

9.06.

oil 9.07.

9.08.

9.09.

9.10.

9.11.

9.12.

9.13.

9.14.

9.15.

oil 9.16.

9.17.

9.18.

9.19.

9.20.

9.21.

oil 9.22.

9.23.

oil 9.24.

oil 9.25.

resin

TABLE 10 (n = 0; intermediates)

Ex.-Nr. Y Z

Phys. Data 10.01. O OMe

10.02. O OMe

10.03. O OMe

10.04. O OMe

10.05. O OMe

10.06. O OMe

10.07. O OMe

10.08. O NHMe

10.09. O OMe

10.10. S NHMe

10.11. S SMe

10.12. SO SMe

10.13. SO SMe

10.14. O OMe

10.15. O SMe

10.16. O OMe

10.17. O NHMe

10.18. O OMe

10.19. S NHMe

10.20. O NHMe

10.21. S SMe

10.22. S SMe

10.23. O OMe

10.24. O OBu(t)

10.25. O OBu(t)

10.26. O OBu(t)

oil

TABLE 11 (n = 0; intermediates)

Ex. Nr Y Z

Phys. Data 11.01. O OCH₃

11.02. O OCH₃

11.03. O OCH₃

11.04. O OCH₃

11.05. O OCH₃

11.06. O OCH₃

11.07. O OCH₃

11.08. O NHCH₃

11.09. S NHCH₃

11.10. S NHCH₃

11.11. S SCH₃

11.12. SO SCH₃

11.13. SO SCH₃

11.14. O SCH₃

11.15. O SCH₃

11.16. O OCH₃

11.17. O NHCH₃

11.18. O NHCH₃

11.19. S NHCH₃

11.20. O NHCH₃

11.21. S SCH₃

11.22. S SCH₃

11.23. O OBu(t)

oil

TABLE 12 (n = 0; intermediates)

Ex. Nr. Z R₂₁ R₂₂

Phys. Data 12.01. OCH₃ CH₃ CH₃

12.02. OCH₃ CH₃ CH₃

12.03. OCH₃ CH₃ CH₃

12.04. OCH₃ CH₃ CH₃

12.05. OCH₃ CH₃ CH₃

12.06. OCH₃ CH₃ CH₃

12.07. OCH₃ CH₃ CH₃

12.08. OCH₃ CH₃ CH₃

12.09. OCH₃ CH₃ CH₃

12.10. OCH₃ CH₃ CH₃

12.11. OCH₃ CH₃ CH₃

12.12. OCH₃ CH₃ CH₃

12.13. OCH₃ CH₃ CH₃

12.14. OCH₃ CH₃ CH₃ 12.15. OCH₃ CH₃ CH₃

12.16. OCH₃ CH₃ CH₃

12.17. OCH₃ CH₃ CH₃

12.18. OCH₃ CH₃ CH₃

12.19. OCH₃ CH₃ CH₃

12.20. OCH₃ CH₃ CH₃

12.21. OCH₃ CH₃ CH₃

12.22. OCH₃ CH₃ CH₃

12.23. OCH₃ CH₃ CH₃

12.24. OCH₃ CH₃ CH₃

12.25. OCH₃ CH₃ CH₃

12.26. OCH₃ CH₃ CH₃

12.27. OCH₃ CH₃ CH₃

12.28. OCH₃ CH₃ CH₃

12.29. OCH₃ CH₃ CH₃

12.30. OCH₃ CH₃ CH₃

12.31. OCH₃ CH₃ CH₃

12.32. OCH₃ CH₃ CH₃

12.33. OCH₃ CH₃ CH₃

12.34. OCH₃ CH₃ CH₃

12.35. OCH₃ CH₃ CH₃

12.36. OCH₃ CH₃ CH₃

12.37. OCH₃ CH₃ CH₃

12.38. OCH₃ CH₃ CH₃

12.39. OCH₃ CH₃ CH₃

12.40. OCH₃ CH₃ CH₃

12.41. OCH₃ CH₃ CH₃

12.42. OCH₃ CH₃ CH₃

12.43. OCH₃ CH₃ CH₃

12.44. OCH₃ CH₃ CH₃

12.45. OCH₃ CH₃ CH₃

12.46. OCH₃ CH₃ CH₃

12.47 OCH₃ CH₃ CH₃

12.48. OCH₃ CH₃ CH₃

12.49. OCH₃ CH₃ CH₃

12.50. OCH₃ CH₃ CH₃

12.51. OCH₃ CH₃ H

12.52. OCH₃ CH₃ H

12.53. OCH₃ CH₃ H

12.54. OCH₃ CH₃ H

12.55. OCH₃ CH₃ H

12.56. OCH₃ H CH₃

12.57. OCH₃ H CH₃

12.58. OCH₃ H CH₃

12.59. OCH₃ H CH₃

12.60. OCH₃ H CH₃

12.61. OCH₃ H H

12.62. OCH₃ H H

12.63. OCH₃ H H

12.64. OCH₃ H H

12.65. OCH₃ H H

12.66. OCH₃ H H

12.67. H H H

12.68. OCH₃ H H

12.69. OCH₃ H H

12.70. OCH₃ H H

12.71. OCH₃ Cl H

12.72. OCH₃ Cl H

12.73. OCH₃ Cl H

12.74. OCH₃ Cl H

12.75. OCH₃ Cl H

12.76. OCH₃ Cl H

12.77. OCH₃ Cl H

12.78. OCH₃ Cl H

12.79. OCH₃ Cl H

12.80. OCH₃ Cl H

12.81. OCH₃ H Cl

12.82. OCH₃ H Cl

12.83. OCH₃ H Cl

12.84. OCH₃ H Cl

12.85. OCH₃ H Cl

12.86. OCH₃ H Cl

12.87. OCH₃ H Cl

12.88. OCH₃ H Cl

12.89. OCH₃ H Cl

12.90. OCH₃ H Cl

12.91. OCH₃ OCH₃ H

12.92. OCH₃ OCH₃ H

12.93. OCH₃ OCH₃ H

12.94. OCH₃ OCH₃ H

12.95. OCH₃ OCH₃ H

12.96. OCH₃ H OCH₃

12.97. OCH₃ H OCH₃

12.98. OCH₃ CH₃ OCH₃

12.99. OCH₃ CH₃ OCH₃

12.100. OCH₃ OCH₃ CH₃

12.101. OCH₃ OCH₃ H

12.102. OCH₃ CH₃ CH₃

12.103. OCH₃ CH₃ CH₃

12.104. OCH₃ CH₃ CH₃

12.105. OCH₃ CH₃ CH₃

12.106. OCH₃ CH₃ CH₃

12.107. OCH₃ CH₃ CH₃

12.108. OCH₃ CH₃ CH₃

12.109. OCH₃ CH₃ CH₃

12.110. OCH₃ CH₃ CH₃

12.111. OCH₃ CH₃ CH₃

12.112. OCH₃ CH₃ CH₃

12.113. OCH₃ CH₃ CH₃

12.114. OCH₃ CH₃ CH₃

12.115. OCH₃ CH₃ CH₃

12.116. OCH₃ CH₃ CH₃

12.117. OCH₃ CH₃ CH₃

12.118. OCH₃ CH₃ CH₃

12.119. OCH₃ CH₃ CH₃

12.120. OCH₃ CH₃ CH₃

12.121. OCH₃ CH₃ CH₃

12.122. OCH₃ CH₃ CH₃

12.123. OCH₃ CH₃ CH₃

12.124. OCH₃ CH₃ CH₃

12.125. OCH₃ CH₃ CH₃

12.126. OCH₃ CH₃ CH₃

12.127. OCH₃ CH₃ CH₃

12.128. OCH₃ CH₃ CH₃

12.129. OCH₃ CH₃ CH₃

12.130. OCH₃ CH₃ CH₃

12.131. OCH₃ CH₃ CH₃

12.132. OCH₃ CH₃ CH₃

12.133. OCH₃ CH₃ CH₃

12.134. OCH₃ CH₃ CH₃

12.135. OCH₃ CH₃ CH₃

12.136. OCH₃ CH₃ CH₃

12.137. OCH₃ CH₃ CH₃

12.138. OCH₃ CH₃ CH₃

12.139. OCH₃ CH₃ CH₃

12.140. OCH₃ CH₃ CH₃

12.141. OCH₃ CH₃ CH₃

12.142. OCH₃ CH₃ CH₃

12.143. OCH₃ CH₃ CH₃

12.143. OCH₃ CH₃ CH₃

12.144. OCH₃ CH₃ CH₃

12.145. OCH₃ CH₃ CH₃

12.146. OCH₃ CH₃ CH₃

12.147. OCH₃ CH₃ CH₃

12.148. OCH₃ CH₃ CH₃

12.149. OCH₃ CH₃ CH₃

12.150. OCH₃ CH₃ CH₃

12.151. OCH₃ CH₃ CH₃

12.152. OCH₃ CH₃ CH₃

12.153. OCH₃ CH₃ CH₃

12.154. OCH₃ CH₃ CH₃

12.155. OCH₃ CH₃ CH₃

12.156. OCH₃ CH₃ CH₃

12.157. OCH₃ CH₃ CH₃

12.158. OCH₃ CH₃ CH₃

12.159. OCH₃ CH₃ CH₃

12.160. OCH₃ CH₃ CH₃

12.161. H H CH₃

12.162. H H H

12.163. OCH₃ CH₃ CH₃

12.164. OCH₃ CH₃ CH₃

12.165. OCH₃ CH₃ CH₃

12.166. OCH₃ CH₃ CH₃

12.167. OCH₃ CH₃ CH₃

12.168. OCH₃ CH₃ CH₃

12.169. OCH₃ CH₃ CH₃

12.170. OCH₃ CH₃ CH₃

12.171. OBu(t) CH₃ CH₃

oil

TABLE 13 (n = 0, R₈ = H, R₉ = H; intermediates)

Phys. Ex. Nr. R11 R14 R13 Data 13.01. Me Me 4-C₆H₄—C≡C—C₆H₃Cl₂(2′,4′)13.02. Me Me 4-C₆H₄—C≡C—C₆H₅ 13.03. Me Me 4-C₆H₄—C≡C—C₆H₄(OCH₃)(4′)13.04. Me Me 4-C₆H₄—C≡C—C₆H₃(CF₃)(3′,5′) 13.05. Me Me4-C₆H₄—C≡C—C₆H₄(CF₃)(3′) 13.06. Me Me 4-C₆H₄—C≡C—CO—C₆H₄(CF₃)(3′) 13.07.Me Me 4-C₆H₄—C≡C—CO—C₆H₅ 13.08. Me Me 4-C₆H₄—C≡C—CO—C₆H₄(Cl)(3′) 13.09.Me Me 4-C₆H₄—C≡C—C≡C—C₃H₇(i) 13.10. Me Me 4-C₆H₄—C≡C—C≡C—C(CH₃)₂—OH13.11. Me Me 4-C₆H₄—(C≡C)₂—C(CH₃)₂—OCOCH₃ 13.12. Me Me4-C₆H₄—C≡C—C(CH₃)₂—OH 13.13. Me Me 4-C₆H₄—C≡C-Pyrazinyl(2′) 13.14. Me Me4-C₆H₄—C≡C-Pyridyl(3′) 13.15. Me Me 4-C₆H₄—C≡C—CO-Pyridyl(3′) 13.16. MeMe 4-C₆H₄—C≡C-Pyridyl(2′) 13.17. Me Me 4-C₆H₄—C≡C-Pyridyl(4′) 13.18. MeMe 4-C₆H₄—C≡C—C₆H₄(CF₃)(4′) 13.19. Me Me 4-C₆H₄—C≡C—C₆H₄(Cl)(4′) 13.20.Me Me 4-C₆H₄—C≡C—CH₂—OH 13.21. Me Me 4-C₆H₄—C≡C-Pyrimidinyl(2′) 13.22.Me Me 4-C₆H₄—C≡C-Pyrimidinyl(4′) 13.23. Me Me 4-C₆H₄—C≡C-Pyrimidinyl(5′)13.24. Me Me 4-C₆H₄—C≡C—I 13.25. Me Me 4-C₆H₄—C≡C—CH₃ 13.26. Me Me4-C₆H₄—C≡C—Br 13.27. Me Me 4-C₆H₄—C≡C—C₆H₄(Br)(4′) 13.28. Me Me4-C₆H₄—C≡C—C₆H₃(OCH₃)₃(3′,4′,5′) 13.29. Me Me4-C₆H₄—C≡C—C₆H₃(CH₃)₂(3′,5′) 13.30. Me Me 4-C₆H₄—C≡C-Thiazolyl(2′)13.31. Me Me 4-C₆H₄—C≡C-Oxazolyl(2′) 13.32. Me Me 4-C₆H₄—C≡C-Thienyl(2′)13.33. Me Me 4-C₆H₄—C≡C-Thienyl(3′) 13.34. Me Me 4-C₆H₄—C≡C—Et 13.35. MeMe 3-C₆H₄—C≡C—H 13.36. Me Me 2-C₆H₄—C≡C—H 13.37. Me Me 3-C₆H₄—C≡C—CH₃13.38. Me Me 2-C₆H₄—C≡C—Br 13.39. Me Me 2-C₆H₄—C≡C—C(CH₃)₂—OH 13.40. MeMe 3-C₆H₄—C≡C—C(CH₃)₂—OH 13.41. Me Me 4-C₆H₄—C≡C—CF₃ 13.42. Me Me4-C₆H₄—C≡C—COOEt 13.43. Me Me 4-C₆H₄—C≡C—COOMe 13.44. Me Me2-C₆H₄—C≡C—C(CH₃)₂—OH 13.45. Me Me 4-C₆H₄—C≡C—C(CH₃)₂—O—CH₃ 13.46. Me Me3-C₆H₄—C≡C—C(CH₃)₂—O—CH₃ 13.47. Me Me 4-C₆H₄—C≡C—CH₂—OMe 13.48. Me Me4-C₆H₄—C≡C—C₄H₉(n)

TABLE 14

Phys. Ex. Nr. Z R13 Data 14.01. OMe 4-C₆H₄—C≡C—C₆H₃Cl₂(2′,4′) resin14.02. OMe 4-C₆H₄—C≡C—C₆H₅ 142- 144° 14.03. OMe4-C₆H₄—C≡C—C₆H₄(OCH₃)(4′) 14.04. OMe 4-C₆H₄—C≡C—C₆H₃(CF₃)(3′,5′) 14.05.OMe 4-C₆H₄—C≡C—C₆H₄(CF₃)(3′) 14.06. QMe 4-C₆H₄—C≡C—CO—C₆H₄(CF₃)(3′)14.07. OMe 4-C₆H₄—C≡C—CO—C₆H₅ 14.08. OMe 4-C₆H₄—C≡C—CO—C₆H₄(Cl)(3′)14.09. OMe 4-C₆H₄—C≡C—C≡C—C₃H₇(i) 14.10. OMe 4-C₆H₄—C≡C—C≡C—C(CH₃)₂—OH14.11. OMe 4-C₆H₄—(C≡C)₂—C(CH₃)₂—OCOCH₃ 14.12. OMe 4-C₆H₄—C≡C—C(CH₃)₂—OH14.13. OMe 4-C₆H₄—C≡C-Pyrazinyl(2′) 14.14. OMe 4-C₆H₄—C≡C-Pyridyl(3′)14.15. OMe 4-C₆H₄—C≡C—CO-Pyridyl(3′) 14.16. OMe 4-C₆H₄—C≡C-Pyridyl(2′)142- 144° 14.17. OMe 4-C₆H₄—C≡C-Pyridyl(4′) 14.18. OMe4-C₆H₄—C≡C—C₆H₄(CF₃)(4′) 14.19. OMe 4-C₆H₄—C≡C—C₆H₄(Cl)(4′) 14.20. OMe4-C₆H₄—C≡C—CH₂—OH 14.21. OMe 4-C₆H₄—C≡C-Pyrimidinyl(2′) 14.22. OMe4-C₆H₄—C≡C-Pyrimidinyl(4′) 14.23. OMe 4-C₆H₄—C≡C-Pyrimidinyl(5′) 14.24.OMe 4-C₆H₄—C≡C—I 14.25. OMe 4-C₆H₄—C≡C—CH₃ 14.26. OMe 4-C₆H₄—C≡C—Br14.27. OMe 4-C₆H₄—C≡C—C₆H₄(Br)(4′) 14.28. OMe4-C₆H₄—C≡C—C₆H₃(OCH₃)₃(3′,4′,5′) 14.29. OMe 4-C₆H₄—C≡C—C₆H₃(CH₃)₂(3′,5′)14.30. OMe 4-C₆H₄—C≡C-Thiazol(2′) 14.31. OMe 4-C₆H₄—C≡C-Oxazolyl(2′)14.32. OMe 4-C₆H₄—C≡C-Thienyl(2′) 14.33. OMe 4-C₆H₄—C≡C-Thienyl(3′)14.34. OMe 4-C₆H₄—C≡C—Et 14.35. OMe 3-C₆H₄—C≡C—H 14.36. OMe 2-C₆H₄—C≡C—H14.37. OMe 3-C₆H₄—C≡C—CH₃ 14.38. OMe 2-C₆H₄—C≡C—Br 14.39. OMe2-C₆H₄—C≡C—C(CH₃)₂—OH 14.40. OMe 3-C₆H₄—C≡C—C(CH₃)₂—OH 14.41. OMe4-C₆H₄—C≡C—CF₃ 14.42. OMe 4-C₆H₄—C≡C—COOEt 14.43. OMe 4-C₆H₄—C≡C—COOMe14.44. OMe 2-C₆H₄—C≡C—C(CH₃)₂—OH 14.45. OMe 4-C₆H₄—C≡C—C(CH₃)₂—O—CH₃14.46. OMe 3-C₆H₄—C≡C—C(CH₃)₂—O—CH₃ 14.47. OMe 4-C₆H₄—C≡C—CH₂—OMe 14.48.OMe 4-C₆H₄—C≡C—C₄H₉(n) 14.49. OMe 4-C₆H₄—C≡C—C₃H₇(n) 14.50. OMe4-C₆H₄—C≡C—C₈H₁₇(n) 14.51. NHMe 4-C₆H₄—C≡C—C₆H₃Cl₂(2′,4′) 14.52. NHMe4-C₆H₄—C≡C—C₆H₅ 14.53. NHMe 4-C₆H₄—C≡C—C₆H₄(OCH₃)(4′) 14.54. NHMe4-C₆H₄—C≡C—C₆H₃(CF₃)(3′,5′) 14.55. NHMe 4-C₆H₄—C≡C—C₆H₄(CF₃)(3′) 14.56.NHMe 4-C₆H₄—C≡C—CO—C₆H₄(CF₃)(3′) 14.57. NHMe 4-C₆H₄—C≡C—CO—C₆H₅ 14.58.NHMe 4-C₆H₄—C≡C—CO—C₆H₄(Cl)(3′) 14.59. NHMe 4-C₆H₄—C≡C—C≡C—C₃H₇(i)14.60. NHMe 4-C₆H₄—C≡C—C≡C—C(CH₃)₂—OH 14.61. NHMe4-C₆H₄—(C≡C)₂—C(CH₃)₂—OCOCH₃ 14.62. NHMe 4-C₆H₄—C≡C—C(CH₃)₂—OH 14.63.NHMe 4-C₆H₄—C≡C-Pyrazinyl(2′) 14.64. NHMe 4-C₆H₄—C≡C-Pyridyl(3′) 14.65.NHMe 4-C₆H₄—C≡C—CO-Pyridyl(3′) 14.66. NHMe 4-C₆H₄—C≡C-Pyridyl(2′) 14.67.NHMe 4-C₆H₄—C≡C-Pyridyl(4′) 14.68. NHMe 4-C₆H₄—C≡C—C₆H₄(CF₃)(4′) 14.69.NHMe 4-C₆H₄—C≡C—C₆H₄(Cl)(4′) 14.70. NHMe 4-C₆H₄—C≡C—CH₂—OH 14.71. NHMe4-C₆H₄—C≡C-Pyrimidinyl(2′) 14.72. NHMe 4-C₆H₄—C≡C-Pyrimidinyl(4′) 14.73.NHMe 4-C₆H₄—C≡C-Pyrimidinyl(5′) 14.74. NHMe 4-C₆H₄—C≡C—I 14.75. NHMe4-C₆H₄—C≡C—CH₃ 14.76. NHMe 4-C₆H₄—C≡C—Br 14.77. NHMe4-C₆H₄—C≡C—C₆H₄(Br)(4′) 14.78. NHMe 4-C₆H₄—C≡C—C₆H₄(OCH₃)₃(3′,4′,5′)14.79. NHMe 4-C₆H₄—C≡C—C₆H₃(CH₃)₂(3′,5′) 14.80. NHMe4-C₆H₄—C≡C-Thiazolyl(2′) 14.81. NHMe 4-C₆H₄—C≡C-Oxazolyl(2′) 14.82. NHMe4-C₆H₄—C≡C-Thienyl(2′) 14.83. NHMe 4-C₆H₄—C≡C-Thienyl(3′) 14.84. NHMe4-C₆H₄—C≡C—Et 14.85. NHMe 3-C₆H₄—C≡C—H 14.86. NHMe 2-C₆H₄—C≡C—H 14.87.NHMe 3-C₆H₄—C≡C—CH₃ 14.88. NHMe 2-C₆H₄—C≡C—Br 14.89. NHMe2-C₆H₄—C≡C—C(CH₃)₂—OH 14.90. NHMe 3-C₆H₄—C≡C—C(CH₃)₂—OH 14.91. NHMe4-C₆H₄—C≡C—CF₃ 14.92. NHMe 4-C₆H₄—C≡C—COOEt 14.93. NHMe 4-C₆H₄—C≡C—COOMe14.94. NHMe 2-C₆H₄—C≡C—C(CH₃)₂—OH 14.95. NHMe 4-C₆H₄—C≡C—C(CH₃)₂—O—CH₃14.96. NHMe 3-C₆H₄—C≡C—C(CH₃)₂—O—CH₃ 14.97. NHMe 4-C₆H₄—C≡C—CH₂—OMe14.98. NHMe 4-C₆H₄—C≡C—C₄H₉(n) 14.99. NHMe 4-C₆H₄—C≡C—C₃H₇(n) 14.100.NHMe 4-C₆H₄—C≡C—C₈H₁₇(n) 14.101. NHMe 4-C6H4—C≡C—C6H4(CH3)(3′) 133- 135°14.102. NHMe 4-C6H4—C≡C—CH2-morpholinyl(1) 100- 102° 14.103. NHMe4-C6H4—CH2—CH2—CH2—morpholinyl(1) resin 14.104. NHMe 4-C6H4—C≡C—CH2Cl126- 129° 14.105. OMe 4-C6H4—C≡C—C6H4(CH3)(3′) 127- 130° 14.106. NHMe4-C6H4—C≡C—CH2—O—C6H3(Cl2)(2′,4′) 119- 122° 14.107. NHMe4-C6H4—C≡C—CH2—O—C6H3(CH3)(2′) 96- 98° 14.108. NHMe4-C6H4—C≡C—CH2—O—C6H3(CH3)(3′) 78- 80°

TABLE 15

Phys. Ex. Nr. X R11 R14 R21 R22 Z R13 Data 15.001 N Me Me Me Me OMe4-C₆H₄—CH═CH—C₆H₃Cl₂(2′,4′) 15.002 N Me Me Me Me OMe 4-C₆H₄—CH═CH—C₆H₅15.003 N Me Me Me Me OMe 4-C₆H₄—CH═CH—C₆H₄(OCH₃)(4′) 15.004 N Me Me MeMe OMe 4-C₆H₄—CH═CH—C₆H₃(CF₃)(3′,5′) 15.005 N Me Me Me Me OMe4-C₆H₄—CH═CH—C₆H₄(CF₃)(3′) 15.006 N Me Me Me Me OMe4-C₆H₄—CH═CH—CO—C₆H₄(CF₃)(3′) 15.007 N Me Me Me Me OMe4-C₆H₄—CH═CH—CO—C₆H₅ 15.008 N Me Me Me Me OMe4-C₆H₄—CH═CH—CO—C₆H₄(Cl)(3′) 15.009 N Me Me Me Me OMe4-C₆H₄—CH═CH—C(CH₃)₂—OH 15.010 N Me Me Me Me OMe4-C₆H₄—CH═CH-Pyrazinyl(2′) 15.011 N Me Me Me Me OMe4-C₆H₄—CH═CH-Pyridyl(3′) 15.012 N Me Me Me Me OMe4-C₆H₄—CH═CH—CO-Pyridyl(3′) 15.013 N Me Me Me Me OMe4-C₆H₄—CH═CH-Pyridyl(2′) 15.014 N Me Me Me Me OMe4-C₆H₄—CH═CH-Pyridyl(4′) 15.015 N Me Me Me Me OMe4-C₆H₄—CH═CH—C₆H₄(CF₃)(4′) 15.016 N Me Me Me Me OMe4-C₆H₄—CH═CH—C₆H₄(Cl)(4′) 15.017 N Me Me Me Me OMe 4-C₆H₄—CH═CH—CH₂—OH15.018 N Me Me Me Me OMe 4-C₆H₄—CH═CH-Pyrimidinyl(2′) 15.019 N Me Me MeMe OMe 4-C₆H₄—CH═CH-Pyrimidinyl(4′) 15.020 N Me Me Me Me OMe4-C₆H₄—CH═CH-Pyrimidinyl(5′) 15.021 N Me Me Me Me OMe 4-C₆H₄—CH═CH—I15.022 N Me Me Me Me OMe 4-C₆H₄—CH═CH—CH₃ 15.023 N Me Me Me Me OMe4-C₆H₄—CH═CH—Br 15.024 N Me Me Me Me OMe 4-C₆H₄—CH═CH—C₆H₄(Br)(4′)15.025 N Me Me Me Me OMe 4-C₆H₄—CH═CH—C₆H₂(OCH₃)₃(3′,4′,5′) 15.026 N MeMe Me Me OMe 4-C₆H₄—CH═CH—C₆H₃(CH₃)₂(3′,5′) 15.027 N Me Me Me Me OMe4-C₆H₄—CH═CH-Thiazolyl(2′) 15.028 N Me Me Me Me OMe4-C₆H₄—CH═CH-Oxazolyl(2′) 15.029 N Me Me Me Me OMe4-C₆H₄—CH═CH-Thienyl(2′) 15.030 N Me Me Me Me OMe4-C₆H₄—CH═CH-Thienyl(3′) 15.031 N Me Me Me Me OMe 4-C₆H₄—CH═CH—Et 15.032N Me Me Me Me OMe 3-C₆H₄—CH═CH2 15.033 N Me Me Me Me OMe 2-C₆H₄—CH═CH215.034 N Me Me Me Me OMe 3-C₆H₄—CH═CH—CH₃ 15.035 N Me Me Me Me OMe2-C₆H₄—CH═CH—Br 15.036 N Me Me Me Me OMe 2-C₆H₄—CH═CH—C(CH₃)₂—OH 15.037N Me Me Me Me OMe 3-C₆H₄—CH═CH—(CH₃)₂—OH 15.038 N Me Me Me Me OMe4-C₆H₄—CH═CH—CF₃ 15.039 N Me Me Me Me OMe 4-C₆H₄—CH═CH—COOEt 15.040 N MeMe Me Me OMe 4-C₆H₄—CH═CH—COOMe 15.041 N Me Me Me Me OMe2-C₆H₄—CH═CH—C(CH₃)₂—OH 15.042 N Me Me Me Me OMe4-C₆H₄—CH═CH—C(CH₃)₂—O—CH₃ 15.043 N Me Me Me Me OMe3-C₆H₄—CH═CH—C(CH₃)₂—O—CH₃ 15.044 N Me Me Me Me OMe 4-C₆H₄—CH═CH—CH₂—OMe15.045 N Me Me Me Me OMe 4-C₆H₄—CH═CH—C₄H₉(n) 15.046 N Me Me Me Me OMe4-C₆H₄—CH═CH—C₃H₇(n) 15.047 N Me Me Me Me OMe 4-C₆H₄—CH═CH—C₈H₁₇(n)15.048 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—C₆H₃Cl₂(2′,4′) 15.049 N Me Me MeMe NHMe 4-C₆H₄—CH═CH—C₆H₅ 15.050 N Me Me Me Me NHMe4-C₆H₄—CH═CH—C₆H₄(OCH₃)(4′) 15.051 N Me Me Me Me NHMe4-C₆H₄—CH═CH—C₆H₃(CF₃)(3′,5′) 15.052 N Me Me Me Me NHMe4-C₆H₄—CH═CH—C₆H₄(CF₃)(3′) 15.053 N Me Me Me Me NHMe4-C₆H₄—CH═CH—CO—C₆H₄(CF₃)(3′) 15.054 N Me Me Me Me NHMe4-C₆H₄—CH═CH—CO—C₆H₅ 15.055 N Me Me Me Me NHMe4-C₆H₄—CH═CH—CO—C₆H₄(Cl)(3′) 15.056 N Me Me Me Me NHMe4-C₆H₄—CH═CH—C(CH₃)₂—OH 15.057 N Me Me Me Me NHMe4-C₆H₄—CH═CH-Pyrazinyl(2′) 15.058 N Me Me Me Me NHMe4-C₆H₄—CH═CH-Pyridyl(3′) 15.059 N Me Me Me Me NHMe4-C₆H₄—CH═CH—CO-Pyridyl(3′) 15.060 N Me Me Me Me NHMe4-C₆H₄—CH═CH-Pyridyl(2′) 15.061 N Me Me Me Me NHMe4-C₆H₄—CH═CH-Pyridyl(4′) 15.062 N Me Me Me Me NHMe4-C₆H₄—CH═CH—C₆H₄(CF₃)(4′) 15.063 N Me Me Me Me NHMe4-C₆H₄—CH═CH—C₆H₄(Cl)(4′) 15.064 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—CH₂—OH15.065 N Me Me Me Me NHMe 4-C₆H₄—CH═CH-Pyrimidinyl(2′) 15.066 N Me Me MeMe NHMe 4-C₆H₄—CH═CH-Pyrimidinyl(4′) 15.067 N Me Me Me Me NHMe4-C₆H₄—CH═CH-Pyrimidinyl(5′) 15.068 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—I15.069 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—CH₃ 15.070 N Me Me Me Me NHMe4-C₆H₄—CH═CH—Br 15.071 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—C₆H₄(Br)(4′)15.072 N Me Me Me Me NHMe 4-C₆H₄—CH═CH— C₆H₂(OCH₃)₃(3′,4′,5′) 15.073 NMe Me Me Me NHMe 4-C₆H₄—CH═CH—C₆H₃(CH₃)₂(3′,5′) 15.074 N Me Me Me MeNHMe 4-C₆H₄—CH═CH-Thiazolyl(2′) 15.075 N Me Me Me Me NHMe4-C₆H₄—CH═CH-Oxazolyl(2′) 15.076 N Me Me Me Me NHMe4-C₆H₄—CH═CH-Thienyl(2′) 15.077 N Me Me Me Me NHMe4-C₆H₄—CH═CH-Thienyl(3′) 15.078 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—Et15.079 N Me Me Me Me NHMe 3-C₆H₄—CH═CH₂ 15.080 N Me Me Me Me NHMe2-C₆H₄—CH═CH₂ 15.081 N Me Me Me Me NHMe 3-C₆H₄—CH═CH—CH₃ 15.082 N Me MeMe Me NHMe 2-C₆H₄—CH═CH—Br 15.083 N Me Me Me Me NHMe2-C₆H₄—CH═CH—C(CH₃)₂—OH 15.084 N Me Me Me Me NHMe3-C₆H₄—CH═CH—C(CH₃)₂—OH 15.085 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—CF₃15.086 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—COOEt 15.087 N Me Me Me Me NHMe4-C₆H₄—CH═CH—COOMe 15.088 N Me Me Me Me NHMe 2-C₆H₄—CH═CH—C(CH₃)₂—OH15.089 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—C(CH₃)₂—O—CH₃ 15.090 N Me Me MeMe NHMe 3-C₆H₄—CH═CH—C(CH₃)₂—O—CH₃ 15.091 N Me Me Me Me NHMe4-C₆H₄—CH═CH—CH₂—OMe 15.092 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—C₄H₉(n)15.093 N Me Me Me Me NHMe 4-C₆H₄—CH═CH—C₃H₇(n) 15.094 N Me Me Me Me NHMe4-C₆H₄—CH═CH—C₈H₁₁(n)

TABLE 16

Phys. Ex. Nr. X R11 R14 R21 R22 Z R13 Data 16.001 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—C₆H₃Cl₂(2′,4′) 16.002 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—C₆H₅16.003 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—C₆H₄(OCH₃)(4′) 16.004 N Me Me MeMe OMe 4-C₆ ₄—CH2—CH2—C₆H₃(CF₃)(3′,5′) 16.005 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—C₆H₄(CF₃)(3′) 16.006 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—CO—C₆H₄(CF₃)(3′) 16.007 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—CO—C₆H₅ 16.008 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—CO—C₆H₄(Cl)(3′) 16.009 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—C(CH₃)₂—OH 16.010 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—Pyrazinyl(2′) 16.011 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—Pyridyl(3′) 16.012 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—CO-Pyridyl(3′) 16.013 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—Pyridyl(2′) 16.014 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—Pyridyl(4′) 16.015 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—C₆H₄(CF₃)(4′) 16.016 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—C₆H₄(Cl)(4′) 16.017 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—CH₂—OH16.018 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—Pyrimidinyl(2′) 16.019 N Me MeMe Me OMe 4-C₆ ₄—CH2—CH2—Pyrimidinyl(4′) 16.020 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—Pyrimidinyl(5′) 16.021 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—I16.022 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—CH₃ 16.023 N Me Me Me Me OMe4-C₆ ₄—CH2—CH2—Br 16.024 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—C₆H₄(Br)(4′)16.025 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2— C₆H₂(OCH₃)₃(3′,4′,5′) 16.026 NMe Me Me Me OMe 4-C₆ ₄—CH2—CH2—C₆H2₃(CH₃)₂(3′,5′) 16.027 N Me Me Me MeOMe 4-C₆ ₄—CH2—CH2-Thiazolyl(2′) 16.028 N Me Me Me Me OMe 4-C₆₄—CH2—CH2-Oxazolyl(2′) 16.029 N Me Me Me Me OMe 4-C₆₄—CH2—CH2-Thienyl(2′) 16.030 N Me Me Me Me OMe 4-C₆₄—CH2—CH2-Thienyl(3′) 16.031 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—Et 16.032N Me Me Me Me OMe 3-C₆ ₄—CH2—CH3 16.033 N Me Me Me Me OMe 2-C₆ ₄—CH2—CH316.034 N Me Me Me Me OMe 3-C₆ ₄—CH2—CH2—CH₃ 16.035 N Me Me Me Me OMe2-C₆ ₄—CH2—CH2—Br 16.036 N Me Me Me Me OMe 2-C₆ ₄—CH2—CH2—C(CH₃)₂—OH16.037 N Me Me Me Me OMe 3-C₆ ₄—CH2—CH2—CH₃)₂—OH 16.038 N Me Me Me MeOMe 4-C₆ ₄—CH2—CH2—CF₃ 16.039 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—COOEt16.040 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—COOMe 16.041 N Me Me Me Me OMe2-C₆ ₄—CH2—CH2—C(CH₃)₂—OH 16.042 N Me Me Me Me OMe 4-C₆₄—CH2—CH2—C(CH₃)₂—O—CH₃ 16.043 N Me Me Me Me OMe 3-C₆₄—CH2—CH2—C(CH₃)₂—O—CH₃ 16.044 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—CH2—OMe16.045 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—C₄H₉(n) 16.046 N Me Me Me Me OMe4-C₆ ₄—CH2—CH2—C₃H₇(n) 16.047 N Me Me Me Me OMe 4-C₆ ₄—CH2—CH2—C₈H₁₇(n)16.048 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—C₆H₃Cl₂(2′,4′) 16.049 N Me MeMe Me NHMe 4-C₆ ₄—CH2—CH2—C₆H₅ 16.050 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—C₆H₄(OCH₃)(4′) 16.051 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—C₆H₃(CF₃)(3′,5′) 16.052 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—C₆H₄(CF₃)(3′) 16.053 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—CO-C₆H₄(CF₃)(3′) 16.054 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—CO-C₆H₅ 16.055 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—CO-C₆H₄(Cl)(3′) 16.056 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—C(CH₃)₂—OH 16.057 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—Pyrazinyl(2′) 16.058 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—Pyridyl(3′) 16.059 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—CO-Pyridyl(3′) 16.060 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—Pyridyl(2′) 16.061 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—Pyridyl(4′) 16.062 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—C₆H₄(CF₃)(4′) 16.063 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—C₆H₄(Cl)(4′) 16.064 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—CH2—OH16.065 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—Pyrimidinyl(2′) 16.066 N Me MeMe Me NHMe 4-C₆ ₄—CH2—CH2—Pyrimidinyl(4′) 16.067 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—Pyrimidinyl(5′) 16.068 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—I16.069 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—CH₃ 16.070 N Me Me Me Me NHMe4-C₆ ₄—CH2—CH2—Br 16.071 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—C₆H₄(Br)(4′)16.072 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2— C₆H₂(OCH₃)₃(3′,4′,5′) 16.073 NMe Me Me Me NHMe 4-C₆ ₄—CH2—CH2—C₆H₃(CH₃)₂(3′,5′) 16.074 N Me Me Me MeNHMe 4-C₆ ₄—CH2—CH2-Thiazolyl(2′) 16.075 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2-Oxazolyl(2′) 16.076 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2-Thienyl(2′) 16.077 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2-Thienyl(3′) 16.078 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—Et 16.079N Me Me Me Me NHMe 3-C₆ ₄—CH2—CH3 16.080 N Me Me Me Me NHMe 2-C₆₄—CH2—CH3 16.081 N Me Me Me Me NHMe 3-C₆ ₄—CH2—CH2—CH₃ 16.082 N Me Me MeMe NHMe 2-C₆ ₄—CH2—CH2—Br 16.083 N Me Me Me Me NHMe 2-C₆₄—CH2—CH2—C(CH₃)₂—OH 16.084 N Me Me Me Me NHMe 3-C₆ ₄—CH2—CH2—C(CH₃)₂—OH16.085 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—CF₃ 16.086 N Me Me Me Me NHMe4-C₆ ₄—CH2—CH2—COOEt 16.087 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—COOMe16.088 N Me Me Me Me NHMe 2-C₆ ₄—CH2—CH2—C(CH₃)₂—OH 16.089 N Me Me Me MeNHMe 4-C₆ ₄—CH2—CH2—C(CH₃)₂—O—CH₃ 16.090 N Me Me Me Me NHMe 3-C₆₄—CH2—CH2—C(CH₃)₂—O—CH₃ 16.091 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—CH₂—OMe16.092 N Me Me Me Me NHMe 4-C₆ ₄—CH2—CH2—C₄H₉(n) 16.093 N Me Me Me MeNHMe 4-C₆ ₄—CH2—CH2—C₃H₇(n) 16.094 N Me Me Me Me NHMe 4-C₆₄—CH2—CH2—C₈H₁₇(n)

TABLE 17

Phys. Ex. Nr. X R11 R14 R21 R22 Z R13 Data 17.001 N Me Me Me Me OMe4-C₆H₄—O—CH2—C₆H₃Cl₂(2′,4′) 17.002 N Me Me Me Me OMe 4-C₆H₄—O—CH2—C₆H₅17.003 N Me Me Me Me OMe 4-C₆H₄—O—CH2—C₆H₄(OCH₃)(4′) 17.004 N Me Me MeMe OMe 4-C₆H₄—O—CH2—C₆H₃(CF₃)(3′,5′) 17.005 N Me Me Me Me OMe4-C₆H₄—O—CH2—C₆H₄(CF₃)(3′) 17.006 N Me Me Me Me OMe4-C₆H₄—O—CH2—CO—C₆H₄(CF₃)(3′) 17.007 N Me Me Me Me OMe4-C₆H₄—O—CH2—CO—C₆H₅ 17.008 N Me Me Me Me OMe4-C₆H₄—O—CH2—CO—C₆H₄(Cl)(3′) 17.009 N Me Me Me Me OMe4-C₆H₄—O—CH2—C(CH₃)₂—OH 17.010 N Me Me Me Me OMe4-C₆H₄—O—CH2—Pyrazinyl(2′) 17.011 N Me Me Me Me OMe4-C₆H₄—O—CH2—Pyridyl(3′) 17.012 N Me Me Me Me OMe4-C₆H₄—O—CH2—CO-Pyridyl(3′) 17.013 N Me Me Me Me OMe4-C₆H₄—O—CH2—Pyridyl(2′) 17.014 N Me Me Me Me OMe4-C₆H₄—O—CH2—Pyridyl(4′) 17.015 N Me Me Me Me OMe4-C₆H₄—O—CH2—C₆H₄(CF₃)(4′) 17.016 N Me Me Me Me OMe4-C₆H₄—O—CH2—C₆H₄(Cl)(4′) 17.017 N Me Me Me Me OMe 4-C₆H₄—O—CH2—CH₂—OH17.018 N Me Me Me Me OMe 4-C₆H₄—O—CH2—Pyrimidinyl(2′) 17.019 N Me Me MeMe OMe 4-C₆H₄—O—CH2—Pyrimidinyl(4′) 17.020 N Me Me Me Me OMe4-C₆H₄—O—CH2—Pyrimidinyl(5′) 17.021 N Me Me Me Me OMe 4-C₆H₄—O—CH2—I17.022 N Me Me Me Me OMe 4-C₆H₄—O—CH2—CH₃ 17.023 N Me Me Me Me OMe4-C₆H₄—O—CH2—Br 17.024 N Me Me Me Me OMe 4-C₆H₄—O—CH2—C₆H₄(Br)(4′)17.025 N Me Me Me Me OMe 4-C₆H₄—O—CH2—C₆H₂(OCH₃)₃(3′,4′,5′) 17.026 N MeMe Me Me OMe 4-C₆H₄—O—CH2—C₆H₃(CH₃)₂(3′,5′) 17.027 N Me Me Me Me OMe4-C₆H₄—O—CH2-Thiazolyl(2′) 17.028 N Me Me Me Me OMe4-C₆H₄—O—CH2-Oxazolyl(2′) 17.029 N Me Me Me Me OMe4-C₆H₄—O—CH2-Thienyl(2′) 17.030 N Me Me Me Me OMe4-C₆H₄—O—CH2-Thienyl(3′) 17.031 N Me Me Me Me OMe 4-C₆H₄—O—CH2—Et 17.032N Me Me Me Me OMe 3-C₆H₄—O—CH3 17.033 N Me Me Me Me OMe 2-C₆H₄—O—CH317.034 N Me Me Me Me OMe 3-C₆H₄—O—CH2—CH3 17.035 N Me Me Me Me OMe2-C₆H₄—O—CH2—Br 17.036 N Me Me Me Me OMe 2-C₆H₄—O—CH2—C(CH₃)₂—OH 17.037N Me Me Me Me OMe 3-C₆H₄—O—CH2—(CH₃)₂—OH 17.038 N Me Me Me Me OMe4-C₆H₄—O—CH2—CF₃ 17.039 N Me Me Me Me OMe 4-C₆H₄—O—CH2—COOEt 17.040 N MeMe Me Me OMe 4-C₆H₄—O—CH2—COOMe 17.041 N Me Me Me Me OMe2-C₆H₄—O—CH2—C(CH₃)₂—OH 17.042 N Me Me Me Me OMe4-C₆H₄—O—CH2—C(CH₃)₂—O—CH₃ 17.043 N Me Me Me Me OMe3-C₆H₄—O—CH2—C(CH₃)₂—O—CH₃ 17.044 N Me Me Me Me OMe 4-C₆H₄—O—CH2—CH₂—OMe17.045 N Me Me Me Me OMe 4-C₆H₄—O—CH2—C₄H₉(n) 17.046 N Me Me Me Me OMe4-C₆H₄—O—CH2—C₃H₇(n) 17.047 N Me Me Me Me OMe 4-C₆H₄—O—CH2—C₈H₁₇(n)17.048 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—C₆H₃Cl₂(2′,4′) 17.049 N Me Me MeMe NHMe 4-C₆H₄—O—CH2—C₆H₅ 17.050 N Me Me Me Me NHMe4-C₆H₄—O—CH2—C₆H₄(OCH₃)(4′) 17.051 N Me Me Me Me NHMe4-C₆H₄—O—CH2—C₆H₃(CF₃)(3′,5′) 17.052 N Me Me Me Me NHMe4-C₆H₄—O—CH2—C₆H₄(CF₃)(3′) 17.053 N Me Me Me Me NHMe4-C₆H₄—O—CH2—CO—C₆H₄(CF₃)(3′) 17.054 N Me Me Me Me NHMe4-C₆H₄—O—CH2—CO—C₆H₅ 17.055 N Me Me Me Me NHMe4-C₆H₄—O—CH2—CO—C₆H₄(Cl)(3′) 17.056 N Me Me Me Me NHMe4-C₆H₄—O—CH2—C(CH₃)₂—OH 17.057 N Me Me Me Me NHMe4-C₆H₄—O—CH2—Pyrazinyl(2′) 17.058 N Me Me Me Me NHMe4-C₆H₄—O—CH2—Pyridyl(3′) 17.059 N Me Me Me Me NHMe4-C₆H₄—O—CH2—CO-Pyridyl(3′) 17.060 N Me Me Me Me NHMe4-C₆H₄—O—CH2—Pyridyl(2′) 17.061 N Me Me Me Me NHMe4-C₆H₄—O—CH2—Pyridyl(4′) 17.062 N Me Me Me Me NHMe4-C₆H₄—O—CH2—C₆H₄(CF₃)(4′) 17.063 N Me Me Me Me NHMe4-C₆H₄—O—CH2—C₆H₄(Cl)(4′) 17.064 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—CH₂—OH17.065 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—Pyrimidinyl(2′) 17.066 N Me Me MeMe NHMe 4-C₆H₄—O—CH2—Pyrimidinyl(4′) 17.067 N Me Me Me Me NHMe4-C₆H₄—O—CH2—Pyrimidinyl(5′) 17.068 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—I17.069 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—CH₃ 17.070 N Me Me Me Me NHMe4-C₆H₄—O—CH2—Br 17.071 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—C₆H₄(Br)(4′)17.072 N Me Me Me Me NHMe 4-C₆H₄—O—CH2— C₆H₂(OCH₃)₃(3′,4′,5′) 17.073 NMe Me Me Me NHMe 4-C₆H₄—O—CH2—C₆H₃(CH₃)₂(3′,5′) 17.074 N Me Me Me MeNHMe 4-C₆H₄—O—CH2-Thiazolyl(2′) 17.075 N Me Me Me Me NHMe4-C₆H₄—O—CH2-Oxazolyl(2′) 17.076 N Me Me Me Me NHMe4-C₆H₄—O—CH2-Thienyl(2′) 17.077 N Me Me Me Me NHMe4-C₆H₄—O—CH2-Thienyl(3′) 17.078 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—Et17.079 N Me Me Me Me NHMe 3-C₆H₄—O—CH3 17.080 N Me Me Me Me NHMe2-C₆H₄—O—CH3 17.081 N Me Me Me Me NHMe 3-C₆H₄—O—CH2—CH3 17.082 N Me MeMe Me NHMe 2-C₆H₄—O—CH2—Br 17.083 N Me Me Me Me NHMe2-C₆H₄—O—CH2—C(CH₃)₂—OH 17.084 N Me Me Me Me NHMe3-C₆H₄—O—CH2—C(CH₃)₂—OH 17.085 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—CF₃17.086 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—COOEt 17.087 N Me Me Me Me NHMe4-C₆H₄—O—CH2—COOMe 17.088 N Me Me Me Me NHMe 2-C₆H₄—O—CH2—C(CH₃)₂—OH17.089 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—C(CH₃)₂—O—CH3 17.090 N Me Me MeMe NHMe 3-C₆H₄—O—CH2—C(CH₃)₂—O—CH3 17.091 N Me Me Me Me NHMe4-C₆H₄—O—CH2—CH₂—OMe 17.092 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—C₄H₉(n)17.093 N Me Me Me Me NHMe 4-C₆H₄—O—CH2—C₃H₇(n) 17.094 N Me Me Me Me NHMe4-C₆H₄—O—CH2—C₈H₁₇(n)

TABLE 18

Phys. Ex. Nr. X R11 R14 R21 R22 Z R13 Data 18.001 N Me Me Me Me OMe4-C₆H₄—O—C₆H₃Cl₂(2′,4′) 18.002 N Me Me Me Me OMe 4-C₆H₄—O—C₆H₅ 18.003 NMe Me Me Me OMe 4-C₆H₄—O—C₆H₄(OCH₃)(4′) 18.004 N Me Me Me Me OMe4-C₆H₄—O—C₆H₃(CF₃)(3′,5′) 18.005 N Me Me Me Me OMe4-C₆H₄—O—C₆H₄(CF₃)(3′) 18.006 N Me Me Me Me OMe4-C₆H₄—O—CO—C₆H₄(CF₃)(3′) 18.007 N Me Me Me Me OMe 4-C₆H₄—O—CO—C₆H₅18.008 N Me Me Me Me OMe 4-C₆H₄—O—CO—C₆H₄(Cl)(3′) 18.009 N Me Me Me MeOMe 4-C₆H₄—O—C₆H₃(CN)(3′)(NO₂)(4′) 18.010 N Me Me Me Me OMe4-C₆H₄—O-Pyrazinyl(2′) 18.011 N Me Me Me Me OMe 4-C₆H₄—O-Pyridyl(3′)18.012 N Me Me Me Me OMe 4-C₆H₄—O—CO-Pyridyl(3′) 18.013 N Me Me Me MeOMe 4-C₆H₄—O-Pyridyl(2′) 18.014 N Me Me Me Me OMe 4-C₆H₄—O-Pyridyl(4′)18.015 N Me Me Me Me OMe 4-C₆H₄—O—C₆H₄(CF₃)(4′) 18.016 N Me Me Me Me OMe4-C₆H₄—O—C₆H₄(Cl)(4′) 18.017 N Me Me Me Me OMe 4-C₆H₄—O—C₆H₄(NO₂)(4′)18.018 N Me Me Me Me OMe 4-C₆H₄—O-Pyrimidinyl(2′) 18.019 N Me Me Me MeOMe 4-C₆H₄—O-Pyrimidinyl(4′) 18.020 N Me Me Me Me OMe4-C₆H₄—O-Pyrimidinyl(5′) 18.021 N Me Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₄—(OMe)(4′) 18.022 N Me Me Me Me OMe 4-C₆H₄—O—CH₃18.023 N Me Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(CF₃)(3′) 18.024 N Me Me MeMe OMe 4-C₆H₄—O—C₆H₄(Br)(4′) 18.025 N Me Me Me Me OMe4-C₆H₄—O—C₆H₂(OCH₃)₃(3′,4′,5′) 18.026 N Me Me Me Me OMe4-C₆H₄—O—C₆H₃(CH₃)₂(3′,5′) 18.027 N Me Me Me Me OMe4-C₆H₄—O-Thiazolyl(2′) 18.028 N Me Me Me Me OMe 4-C₆H₄—O-Oxazolyl(2′)18.029 N Me Me Me Me OMe 4-C₆H₄—O-Thienyl(2′) 18.030 N Me Me Me Me OMe4-C₆H₄—O-Thienyl(3′) 18.031 N Me Me Me Me OMe 4-C₆H₄—O—Et 18.032 N Me MeMe Me OMe 3-C₆H₄—O—H 18.033 N Me Me Me Me OMe 2-C₆H₄—O—H 18.034 N Me MeMe Me OMe 3-C₆H₄—O—CH₃ 18.035 N Me Me Me Me OMe4-C₆H₄—O—CO-NH-C₆H₄—(Cl)(4′) 18.036 N Me Me Me Me OMe4-C₆H₄—O—CO-NH-C₆H₃-(Cl₂)(2′,4′) 18.037 N Me Me Me Me OMe4-C₆H₄—O—CO-NH-C₆H₄—(NO₂)(4′) 18.038 N Me Me Me Me OMe 4-C₆H₄—O—CF₃18.039 N Me Me Me Me OMe 4-C₆H₄—O—COOEt 18.040 N Me Me Me Me OMe4-C₆H₄—O—COOMe 18.041 N Me Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(Br)(4′)18.042 N Me Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(I)(4′) 18.043 N Me Me MeMe OMe 4-C₆H₄—O—CO—NH—C₆H₄—(CH₃)(2′) 18.044 N Me Me Me Me OMe4-C₆H₄—O—CH₂—OMe 18.045 N Me Me Me Me OMe 4-C₆H₄—O—C₄H₉(n) 18.046 N MeMe Me Me OMe 4-C₆H₄—O—C₃H₇(n) 18.047 N Me Me Me Me OMe 4-C₆H₄—O—C₈H₁₇(n)18.048 N Me Me Me Me NHMe 4-C₆H₄—O—C₆H₃Cl₂(2′,4′) 18.049 N Me Me Me MeNHMe 4-C₆H₄—O—C₆H₅ 18.050 N Me Me Me Me NHMe 4-C₆H₄—O—C₆H₄(OCH₃)(4′)18.051 N Me Me Me Me NHMe 4-C₆H₄—O—C₆H₃(CF₃)(3′,5′) 18.052 N Me Me Me MeNHMe 4-C₆H₄—O—C₆H₄(CF₃)(3′) 18.053 N Me Me Me Me NHMe4-C₆H₄—O—CO—C₆H₄(CF₃)(3′) 18.054 N Me Me Me Me NHMe 4-C₆H₄—O—CO—C₆H₅18.055 N Me Me Me Me NHMe 4-C₆H₄—O—CO—C₆H₄(Cl)(3′) 18.056 N Me Me Me MeOMe 4-C₆H₄—O—CO—NH—C₆H₃—(CH₃)₂(2′,6′) 18.057 N Me Me Me Me NHMe4-C₆H₄—O-Pyrazinyl(2′) 18.058 N Me Me Me Me NHMe 4-C₆H₄—O-Pyridyl(3′)18.059 N Me Me Me Me NHMe 4-C₆H₄—O—CO-Pyridyl(3′) 18.060 N Me Me Me MeNHMe 4-C₆H₄—O-Pyridyl(2′) 18.061 N Me Me Me Me NHMe 4-C₆H₄—O-Pyridyl(4′)18.062 N Me Me Me Me NHMe 4-C₆H₄—O—C₆H₄(CF₃)(4′) 18.063 N Me Me Me MeNHMe 4-C₆H₄—O—C₆H₄(Cl)(4′) 18.064 N Me Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₃—(Me)(2′)(Et)(6′) 18.065 N Me Me Me Me NHMe 4-C₆H₄O-Pyrimidinyl(2′)18.066 N Me Me Me Me NHMe 4-C₆H₄—O-Pyrimidinyl(4′) 18.067 N Me Me Me MeNHMe 4-C₆H₄—O-Pyrimidinyl(5′) 18.068 N Me Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(Me)₂(2′,4′) 18.069 N Me Me Me Me NHMe 4-C₆H₄—O—CH₃18.070 N Me Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(Cl)(3′) 18.071 N Me Me MeMe NHMe 4-C₆H₄—O—C₆H₄(Br)(4′) 18.072 N Me Me Me Me NHMe4-C₆H₄—O—C₆H₂(OCH₃)₃(3′,4′,5′) 18.073 N Me Me Me Me NHMe4-C₆H₄—O—C₆H₃(CH₃)₂(3′,5′) 18.074 N Me Me Me Me NHMe4-C₆H₄—O-Thiazolyl(2′) 18.075 N Me Me Me Me NHMe 4-C₆H₄—O-Oxazolyl(2′)18.076 N Me Me Me Me NHMe 4-C₆H₄—O-Thienyl(2′) 18.077 N Me Me Me Me NHMe4-C₆H₄—O-Thienyl(3′) 18.078 N Me Me Me Me NHMe 4-C₆H₄—O—Et 18.079 N MeMe Me Me NHMe 3-C₆H₄—O—CH3 18.080 N Me Me Me Me NHMe 2-C₆H₄—O—CH3 18.081N Me Me Me Me NHMe 3-C₆H₄—O—CH₃ 18.082 N Me Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₄—(Cl)(2′) 18.083 N Me Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(Cl)2(3′,5′) 18.084 N Me Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃(CF₃)₂(3′,5′) 18.085 N Me Me Me Me NHMe 4-C₆H₄—O—CF₃18.086 N Me Me Me Me NHMe 4-C₆H₄—O—COOEt 18.087 N Me Me Me Me NHMe4-C₆H₄—O—COOMe 18.088 N Me Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(CF₃)(4′)18.089 N Me Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(OCH₃)(4′) 18.056 N Me MeMe Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(OCF₃)(4′) 18.091 N Me Me Me Me NHMe4-C₆H₄—O—CH₂—OMe 18.092 N Me Me Me Me NHMe 4-C₆H₄—O—C₄H₉(n) 18.093 N MeMe Me Me NHMe 4-C₆H₄—O—C₃H₇(n) 18.094 N Me Me Me Me NHMe4-C₆H₄—O—C₈H₁₇(n)

TABLE 19

Phys. Ex. Nr. X R11 R14 R21 R22 Z R13 Data 19.001 N Me Et Me Me OMe4-C₆H₄—O—C₆H₃Cl₂(2′,4′) 19.002 N Me Et Me Me OMe 4-C₆H₄—O—C₆H₅ 19.003 NMe Et Me Me OMe 4-C₆H₄—O—C₆H₄(OCH₃)(4′) 19.004 N Me Et Me Me OMe4-C₆H₄—O—C₆H₃(CF₃)(3′,5′) 19.005 N Me Et Me Me OMe4-C₆H₄—O—C₆H₄(CF₃)(3′) 19.006 N Me Et Me Me OMe4-C₆H₄—O—CO—C₆H₄(CF₃)(3′) 19.007 N Me Et Me Me OMe 4-C₆H₄—O—CO—C₆H₅19.008 N Me Et Me Me OMe 4-C₆H₄—O—CO—C₆H₄(Cl)(3′) 19.009 N Me Et Me MeOMe 4-C₆H₄—O—C₆H₃(CN)(3′)(NO₂)(4′) 19.010 N Me Et Me Me OMe4-C₆H₄—O-Pyrazinyl(2′) 19.011 N Me Et Me Me OMe 4-C₆H₄—O-Pyridyl(3′)19.012 N Me Et Me Me OMe 4-C₆H₄—O—CO-Pyridyl(3′) 19.013 N Me Et Me MeOMe 4-C₆H₄—O-Pyridyl(2′) 19.014 N Me Et Me Me OMe 4-C₆H₄—O-Pyridyl(4′)19.015 N Me Et Me Me OMe 4-C₆H₄—O—C₆H₄(CF₃)(4′) 19.016 N Me Et Me Me OMe4-C₆H₄—O—C₆H₄(Cl)(4′) 19.017 N Me Et Me Me OMe 4-C₆H₄—O—C₆H₄(NO₂)(4′)19.018 N Me Et Me Me OMe 4-C₆H₄—O-Pyrimidinyl(2′) 19.019 N Me Et Me MeOMe 4-C₆H₄—O-Pyrimidinyl(4′) 19.020 N Me Et Me Me OMe4-C₆H₄—O-Pyrimidinyl(5′) 19.021 N Me Et Me Me OMe4-C₆H₄—O—CO—NH—C₆H₄—(OMe)(4′) 19.022 N Me Et Me Me OMe 4-C₆H₄—O—CH₃19.023 N Me Et Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(CF₃)(3′) 19.024 N Me Et MeMe OMe 4-C₆H₄—O—C₆H₄(Br)(4′) 19.025 N Me Et Me Me OMe4-C₆H₄—O—C₆H₂(OCH₃)₃(3′,4′,5′) 19.026 N Me Et Me Me OMe4-C₆H₄—O—C₆H₃(CH₃)₂(3′,5′) 19.027 N Me Et Me Me OMe4-C₆H₄—O-Thiazolyl(2′) 19.028 N Me Et Me Me OMe 4-C₆H₄—O-Oxazolyl(2′)19.029 N Me Et Me Me OMe 4-C₆H₄—O-Thienyl(2′) 19.030 N Me Et Me Me OMe4-C₆H₄—O-Thienyl(3′) 19.031 N Me Et Me Me OMe 4-C₆H₄—O—Et 19.032 N Me EtMe Me OMe 3-C₆H₄—O—H 19.033 N Me Et Me Me OMe 2-C₆H₄—O—H 19.034 N Me EtMe Me OMe 3-C₆H₄—O—CH₃ 19.035 N Me Et Me Me OMe4-C₆H₄—O—CO—NH—C₆H₄—(Cl)(4′) 19.036 N Me Et Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(Cl₂)(2′,4′) 19.037 N Me Et Me Me OMe4-C₆H₄—O—CO—NH—C₆H₄—(NO₂)(4′) 19.038 N Me Et Me Me OMe 4-C₆H₄—O—CF₃19.039 N Me Et Me Me OMe 4-C₆H₄—O—COOEt 19.040 N Me Et Me Me OMe4-C₆H₄—O—COOMe 19.041 N Me Et Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(Br)(4′)19.042 N Me Et Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(I)(4′) 19.043 N Me Et MeMe OMe 4-C₆H₄—O—CO—NH—C₆H₄—(CH₃)(2′) 19.044 N Me Et Me Me OMe4-C₆H₄—O—CH₂—OMe 19.045 N Me Et Me Me OMe 4-C₆H₄—O—C₄H₉(n) 19.046 N MeEt Me Me OMe 4-C₆H₄—O—C₃H₇(n) 19.047 N Me Et Me Me OMe4-C₆H₄—O—C₆H_(17(n)) 19.048 N Me Et Me Me NHMe 4-C₆H₄—O—C₆H₃Cl₂(2′,4′)19.049 N Me Et Me Me NHMe 4-C₆H₄—O—C₆H₅ 19.050 N Me Et Me Me NHMe4-C₆H₄—O—C₆H₄(OCH₃)(4′) 19.051 N Me Et Me Me NHMe4-C₆H₄—O—C₆H₃(CF₃)(3′,5′) 19.052 N Me Et Me Me NHMe4-C₆H₄—O—C₆H₄(CF₃)(3′) 19.053 N Me Et Me Me NHMe4-C₆H₄—O—CO—C₆H₄(CF₃)(3′) 19.054 N Me Et Me Me NHMe 4-C₆H₄—O—CO—C₆H₅19.055 N Me Et Me Me NHMe 4-C₆H₄—O—CO—C₆H₄(Cl)(3′) 19.056 N Me Et Me MeOMe 4-C₆H₄—O—CO—NH—C₆H₃—(CH₃)₂(2′,6′) 19.057 N Me Et Me Me NHMe4-C₆H₄—O-Pyrazinyl(2′) 19.058 N Me Et Me Me NHMe 4-C₆H₄—O-Pyridyl(3′)19.059 N Me Et Me Me NHMe 4-C₆H₄—O—CO-Pyridyl(3′) 19.060 N Me Et Me MeNHMe 4-C₆H₄—O-Pyridyl(2′) 19.061 N Me Et Me Me NHMe 4-C₆H₄—O-Pyridyl(4′)19.062 N Me Et Me Me NHMe 4-C₆H₄—O—C₆H₄(CF₃)(4′) 19.063 N Me Et Me MeNHMe 4-C₆H₄—O—C₆H₄(Cl)(4′) 19.064 N Me Et Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₃—(Me)(2′)(Et)(6′) 19.065 N Me Et Me Me NHMe 4-C₆H₄—O-Pyrimidinyl(2′)19.066 N Me Et Me Me NHMe 4-C₆H₄—O-Pyrimidinyl(4′) 19.067 N Me Et Me MeNHMe 4-C₆H₄—O-Pyrimidinyl(5′) 19.068 N Me Et Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(Me)₂(2′,4′) 19.069 N Me Et Me Me NHMe 4-C₆H₄—O—CH₃19.070 N Me Et Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(Cl)(3′) 19.071 N Me Et MeMe NHMe 4-C₆H₄—O—C₆H₄(Br)(4′) 19.072 N Me Et Me Me NHMe4-C₆H₄—O—C₆H₂(OCH₃)₃(3′,4′,5′) 19.073 N Me Et Me Me NHMe4-C₆H₄—O—C₆H₃(CH₃)₂(3′,5′) 19.074 N Me Et Me Me NHMe4-C₆H₄—O-Thiazolyl(2′) 19.075 N Me Et Me Me NHMe 4-C₆H₄—O-Oxazolyl(2′)19.076 N Me Et Me Me NHMe 4-C₆H₄—O-Thienyl(2′) 19.077 N Me Et Me Me NHMe4-C₆H₄—O-Thienyl(3′) 19.078 N Me Et Me Me NHMe 4-C₆H₄—O—Et 19.079 N MeEt Me Me NHMe 3-C₆H₄—O—CH3 19.080 N Me Et Me Me NHMe 2-C₆H₄—O—CH3 19.081N Me Et Me Me NHMe 3-C₆H₄—O—CH3 19.082 N Me Et Me Me OMe4-C₆H₄—O—CO—NH—C₆H₄—(Cl)(2′) 19.083 N Me Et Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(Cl)2(3′,5′) 19.084 N Me Et Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(CF₃)₂(3′,5′) 19.085 N Me Et Me Me NHMe 4-C₆H₄—O—CF₃19.086 N Me Et Me Me NHMe 4-C₆H₄—O—COOEt 19.087 N Me Et Me Me NHMe4-C₆H₄—O—COOMe 19.088 N Me Et Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(CF₃)(4′)19.089 N Me Et Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(OCH₃)(4′) 19.056 N Me EtMe Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(OCF₃)(4′) 19.091 N Me Et Me Me NHMe4-C₆H₄—O—CH₂—OMe 19.092 N Me Et Me Me NHMe 4-C₆H₄—O—C₄H₉(n) 19.093 N MeEt Me Me NHMe 4-C₆H₄—O—C₃H₇(n) 19.094 N Me Et Me Me NHMe4-C₆H₄—O—C₈H₁₇(n)

TABLE 20

Phys. Ex. Nr. X R11 R21 R22 Z R13 Data 20.001 N Me Me Me OMe4-C₆H₄—O—C₆H₃Cl₂(2′,4′) 20.002 N Me Me Me OMe 4-C₆H₄—O—C₆H₅ 20.003 N MeMe Me OMe 4-C₆H₄—O—C₆H₄(OCH₃)(4′) 20.004 N Me Me Me OMe4-C₆H₄—O—C₆H₃(CF₃)(3′,5′) 20.005 N Me Me Me OMe 4-C₆H₄—O—C₆H₄(CF₃)(3′)20.006 N Me Me Me OMe 4-C₆H₄—O—CO—C₆H₄(CF₃)(3′) 20.007 N Me Me Me OMe4-C₆H₄—O—CO—C₆H₅ 20.008 N Me Me Me OMe 4-C₆H₄—O—CO—C₆H₄(Cl)(3′) 20.009 NMe Me Me OMe 4-C₆H₄—O—C₆H₃(CN)(3′)(NO₂)(4′) 20.010 N Me Me Me OMe4-C₆H₄—O-Pyrazinyl(2′) 20.011 N Me Me Me OMe 4-C₆H₄—O-Pyridyl(3′) 20.012N Me Me Me OMe 4-C₆H₄—O—CO-Pyridyl(3′) 20.013 N Me Me Me OMe4-C₆H₄—O-Pyridyl(2′) 20.014 N Me Me Me OMe 4-C₆H₄—O-Pyridyl(4′) 20.015 NMe Me Me OMe 4-C₆H₄—O—C₆H₄(CF₃)(4′) 20.016 N Me Me Me OMe4-C₆H₄—O—C₆H₄(Cl)(4′) 20.017 N Me Me Me OMe 4-C₆H₄—O—C₆H₄(NO₂)(4′)20.018 N Me Me Me OMe 4-C₆H₄—O-Pyrimidinyl(2′) 20.019 N Me Me Me OMe4-C₆H₄-O-Pyrimidinyl(4′) 20.020 N Me Me Me OMe 4-C₆H₄—O-Pyrimidinyl(5′)20.021 N Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(OMe)(4′) 20.022 N Me Me MeOMe 4-C₆H₄—O—CH₃ 20.023 N Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(CF₃)(3′)20.024 N Me Me Me OMe 4-C₆H₄—O—C₆H₄(Br)(4′) 20.025 N Me Me Me OMe4-C₆H₄—O—C₆H₂(OCH₃)₃(3′,4′,5′) 20.026 N Me Me Me OMe 4-C₆H_(4-O—C)₆H₃(CH₃)₂(3′,5′) 20.027 N Me Me Me OMe 4-C₆H₄—O-Thiazolyl(2′) 20.028 NMe Me Me OMe 4-C₆H₄—O-Oxazolyl(2′) 20.029 N Me Me Me OMe4-C₆H₄—O-Thienyl(2′) 20.030 N Me Me Me OMe 4-C₆H₄—O-Thienyl(3′) 20.031 NMe Me Me OMe 4-C₆H₄—O—Et 20.032 N Me Me Me OMe 3-C₆H₄—O—H 20.033 N Me MeMe OMe 2-C₆H₄—O—H 20.034 N Me Me Me OMe 3-C₆H₄—O—CH₃ 20.035 N Me Me MeOMe 4-C₆H₄—O—CO—NH—C₆H₄—(Cl)(4′) 20.036 N Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(Cl₂)(2′,4′) 20.037 N Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₄—(NO₂)(4′) 20.038 N Me Me Me OMe 4-C₆H₄—O—CF₃ 20.039N Me Me Me OMe 4-C₆H₄—O—COOEt 20.040 N Me Me Me OMe 4-C₆H₄—O—COOMe20.041 N Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(Br)(4′) 20.042 N Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₄—(I)(4′) 20.043 N Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₄—(CH₃)(2′) 20.044 N Me Me Me OMe 4-C₆H₄—O—CH₂—OMe20.045 N Me Me Me OMe 4-C₆H₄—O—C₄H₉(n) 20.046 N Me Me Me OMe4-C₆H₄—O—C₃H₇(n) 20.047 N Me Me Me OMe 4-C₆H₄—O—C₈H₁₇(n) 20.048 N Me MeMe NHMe 4-C₆H₄—O—C₆H₃Cl₂(2′,4′) 20.049 N Me Me Me NHMe 4-C₆H₄—O—C₆H₅20.050 N Me Me Me NHMe 4-C₆H₄—O—C₆H₄(OCH₃)(4′) 20.051 N Me Me Me NHMe4-C₆H₄—O—C₆H₃(CF₃)(3′,5′) 20.052 N Me Me Me NHMe 4-C₆H₄—O—C₆H₄(CF₃)(3′)20.053 N Me Me Me NHMe 4-C₆H₄—O—CO—C₆H₄(CF₃)(3′) 20.054 N Me Me Me NHMe4-C₆H₄—O—CO—C₆H₅ 20.055 N Me Me Me NHMe 4-C₆H₄—O—CO—C₆H₄(Cl)(3′) 20.056N Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₃—(CH₃)₂(2′,6′) 20.057 N Me Me Me NHMe4-C₆H₄—O-Pyrazinyl(2′) 20.058 N Me Me Me NHMe 4-C₆H₄-O-Pyridyl(3′)20.059 N Me Me Me NHMe 4-C₆H₄-O—CO-Pyridyl(3′) 20.060 N Me Me Me NHMe4-C₆H₄-O-Pyridyl(2′) 20.061 N Me Me Me NHMe 4-C₆H₄—O-Pyridyl(4′) 20.062N Me Me Me NHMe 4-C₆H₄—O—C₆H₄(CF₃)(4′) 20.063 N Me Me Me NHMe4-C₆H₄—O—C₆H₄(Cl)(4′) 20.064 N Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(Me)(2′)(Et)(6′) 20.065 N Me Me Me NHMe4-C₆H₄—O-Pyrimidinyl(2′) 20.066 N Me Me Me NHMe 4-C₆H₄—O-Pyrimidinyl(4′)20.067 N Me Me Me NHMe 4-C₆H₄—O-Pyrimidinyl(5′) 20.068 N Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(Me)₂(2′,4′) 20.069 N Me Me Me NHMe 4-C₆H₄—O—CH₃20.070 N Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(Cl)(3′) 20.071 N Me Me MeNHMe 4-C₆H₄—O—C₆H₄(Br)(4′) 20.072 N Me Me Me NHMe4-C₆H₄—O—C₆H₂(OCH₃)₃(3′,4′,5′) 20.073 N Me Me Me NHMe4-C₆H₄—O—C₆H₃(CH₃)₂(3′,5′) 20.074 N Me Me Me NHMe 4-C₆H₄-O-Thiazolyl(2′)20.075 N Me Me Me NHMe 4-C₆H₄—O-Oxazolyl(2′) 20.076 N Me Me Me NHMe4-C₆H₄—O-Thienyl(2′) 20.077 N Me Me Me NHMe 4-C₆H₄—O-Thienyl(3′) 20.078N Me Me Me NHMe 4-C₆H₄—O—Et 20.079 N Me Me Me NHMe 3-C₆H₄—O—CH3 20.080 NMe Me Me NHMe 2-C₆H₄—O—CH3 20.081 N Me Me Me NHMe 3-C₆H₄—O—CH₃ 20.082 NMe Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(Cl)(2′) 20.083 N Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(Cl)₂(3′,5′) 20.084 N Me Me Me OMe4-C₆H₄—O—CO—NH—C₆H₃—(CF₃)₂(3′,5′) 20.085 N Me Me Me NHMe 4-C₆H₄—O—CF₃20.086 N Me Me Me NHMe 4-C₆H₄—O—COOEt 20.087 N Me Me Me NHMe4-C₆H₄—O—COOMe 20.088 N Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(CF₃)(4′)20.089 N Me Me Me OMe 4-C₆H₄—O—CO—NH—C₆H₄—(OCH₃)(4′) 20.056 N Me Me MeOMe 4-C₆H₄—O—CO—NH—C₆H₄—(OCF₃)(4′) 20.091 N Me Me Me NHMe4-C₆H₄—O—CH₂—OMe 20.092 N Me Me Me NHMe 4-C₆H₄—O—C₄H₉(n) 20.093 N Me MeMe NHMe 4-C₆H₄—O—C₃H₇(n) 20.094 N Me Me Me NHMe 4-C₆H₄—O—C₈H₇(n)

2. Formulation Examples for active ingredients from the Tables(throughout, percentages are by weight

2.1 Wettable powders a) b) c) active ingredient from the Tables 25% 50%75% sodium lignosulfonate  5%  5% — sodium lauryl sulfate  3% —  5%sodium diisobutylnaphthalene sulfonate —  6% 10% octylphenolpolyethylene glycol ether —  2% — (7-8 mol of ethylene oxide) highlydispersed silicic acid  5% 10% 10% kaolin 62% 27% —

The active ingredient is mixed with the adjuvants and the mixture ishomogeneously ground in a suitable mill, affording wettable powderswhich can be diluted with water to give suspensions of any desiredconcentration.

2.2 Emulsifiable concentrate active ingredient from the Tables 10%octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide)calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether 4% (35mol of ethylene oxide) cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution can be obtained from this concentrateby dilution with water.

2.3 Dusts a) b) active ingredient from the Tables  5%  8% talcum 95% —kaolin — 92%

Ready-for-use dusts are obtained by mixing the active ingredient withthe carriers and grinding the mixture in a suitable mill.

2.4 Extruder granules active ingredient from the Tables 10% sodiumlignosulfonate 2% carboxymethylcellulose 1% kaolin 87%

The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

2.5 Coated granules active ingredient from the Tables 3% polyethyleneglycol (mol. wt. 200) 3% kaolin 94%

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

2.6 Suspension concentrate active ingredient from the Tables  40%ethylene glycol  10% nonylphenol polyethylene glycol ether   6% (15 molof ethylene oxide) sodium lignosulfonate  10% carboxymethylcellulose  1% 37% aqueous formaldehyde solution 0.2% silicone oil in the form ofa 75% 0.8% aqueous emulsion water  32%

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water.

BIOLOGICAL EXAMPLES A. Microbicidal Action Example E-1 Action againstPuccinia graminis on Wheat

a) Residual-protective action

6 days after sowing, wheat plants are sprayed to drip point with anaqueous spray mixture (0.02% active ingredient) prepared from a wettablepowder formulation of the test compound and infected 24 hours later witha uredospore suspension of the fungus. After an incubation period of 48hours (conditions: 95 to 100% relative humidity at 20°), the plants areplaced in a greenhouse at 22°. The fungus infestation is evaluated 12days after infection.

b) Systemic Action

5 days after sowing, wheat plants are watered with an aqueous spraymixture (0.006% active ingredient, based on the volume of the soil)prepared from a wettable powder formulation of the test compound. Careis taken that the spray mixture does not come into contact with theparts of the plants above the soil. The plants are infected 48 hourslater with a uredospore suspension of the fungus. After an incubationperiod of 48 hours (conditions: 95 to 100% relative humidity at 20°),the plants are placed in a greenhouse at 22°. The fungus infestation isevaluated 12 days after infection.

Compounds from the Tables exhibit a good activity.

Example E-2 Action Against Phytophthora infestans on Tomatoes

a) Residual-protective Action

After a cultivation period of three weeks, tomato plants are sprayed todrip point with an aqueous spray mixture (0.02% active ingredient)prepared from a wettable powder formulation of the test compound andinfected 24 hours later with a sporangia suspension of the fungus. Thefungus infestation is evaluated 5 days after infection, during whichperiod 90 to 100% relative humidity and a temperature of 200 aremaintained.

b) Systemic Action

After a cultivation period of three weeks, tomato plants are wateredwith an aqueous spray mixture (0.006% active ingredient, based on thevolume of the soil) prepared from a wettable powder formulation of thetest compound. Care is taken that the spray mixture does not come intocontact with the parts of the plants above the soil. The plants areinfected 48 hours later with a sporangia suspension of the fungus. Thefungus infestation is evaluated 5 days after infection, during whichperiod 90 to 100% relative humidity and a temperature of 20° aremaintained.

Compounds from the Tables exhibit a good activity.

Example E-3 Residual-protective Action Against Cercospora arachidicolaon Groundnuts

Groundnut plants 10 to 15 cm in height are sprayed to drip point with anaqueous spray mixture (0.02% active ingredient) prepared from a wettablepowder formulation of the test compound, and infected 48 hours laterwith a conidia suspension of the fungus. The plants are incubated for 72hours at 21° and high humidity and then placed in a greenhouse until thetypical leaf specks appear. The action of the active ingredient isevaluated 12 days after infection and is based on the number and size ofthe leaf specks.

Compounds from the Tables exhibit a good activity.

Example E-4 Action Against Plasmopara viticola on Vines

Vine seedlings at the 4- to 5-leaf stage are sprayed to drip point withan aqueous spray mixture (0.02% active ingredient) prepared from awettable powder formulation of the test compound and infected 24 hourslater with a sporangia suspension of the fungus. The fungus infestationis evaluated 6 days after infection, during which period 95 to 100%relative humidity and a temperature of 20° are maintained.

Compounds from the Tables exhibit a good activity.

Example E-5 Action Against Colletotrichum lagenarium on Cucumbers

After a cultivation period of 2 weeks, cucumber plants are sprayed witha spray mixture (0.002% concentration) prepared from a wettable powderformulation of the test compound. Two days later, the plants areinfected with a spore suspension (1.5×10⁵ spores/ml) of the fungus andincubated for 36 hours at 23° C. and high humidity. Incubation is thencontinued at normal humidity and about 22° C. The fungus infestationthat has occurred is evaluated 8 days after infection.

Compounds from the Tables exhibit a good activity.

Example E-6 Residual-protective Action Against Venturia inaegualis onApples

Apple cuttings with 10 to 20 cm long fresh shoots are sprayed to drippoint with an aqueous spray mixture (0.02% active ingredient) preparedfrom a wettable powder formulation of the test compound, and infected 24hours later with a conidia suspension of the fungus. The plants areincubated for 5 days at 90 to 100% relative humidity and placed in agreenhouse for a further 10 days at 20 to 24°. The fungus infestation isevaluated 12 days after infection.

Compounds from the Tables exhibit a good activity.

Example E-7 Action Against Erysiphe graminis on Barley

a) Residual-protective Action

Barley plants about 8 cm in height are sprayed to drip point with anaqueous spray mixture (0.02% active ingredient) prepared from a wettablepowder formulation of the test compound and dusted 3 to 4 hours laterwith conidia of the fungus. The infected plants are placed in agreenhouse at 22°. The fungus infestation is evaluated 12 days afterinfection.

Compounds from the Tables exhibit a good activity.

b) Systemic Action

Barley plants about 8 cm in height are watered with an aqueous spraymixture (0.002% active ingredient, based on the volume of the soil)prepared from a wettable powder formulation of the test compound. Careis taken that the spray mixture does not come into contact with theparts of the plants above the soil. The plants are dusted 48 hours laterwith conidia of the fungus. The infected plants are placed in agreenhouse at 22°. The fungus infestation is evaluated 12 days afterinfection.

Compounds from the Tables exhibit a good activity.

Example E-8 Action Against Podosphaera leucotricha on Apple Shoots

Apple cuttings with approximately 15 cm long fresh shoots are sprayedwith a spray mixture (0.06% active ingredient). The treated plants areinfected 24 hours later with a conidia suspension of the fungus and areplaced in a controlled environment chamber at 70% relative humidity and20° C. The fungus infestation is evaluated 12 days after infection.

Compounds from the Tables exhibit a good activity.

Biological Examples B. Insecticidal Action Example E-9 Action AgainstAphis craccivora

Pea seedlings are infested with Aphis craccivora, subsequently sprayedwith a spray mixture comprising 100 ppm of the test compound and thenincubated at 20°. 3 and 6 days later the percentage reduction inpopulation (% activity) is determined by comparing the number of deadaphids on the treated plants with that on untreated plants.

Compounds of the Tables exhibit a good activity in this test, that is tosay a mortality rate of more than 80%.

Example E-10 Action Against Diabrotica balteata

Maize seedlings are sprayed with an aqueous emulsion spray mixturecomprising 100 ppm of the test compound. After the spray-coating hasdried, the maize seedlings are populated with 10 Diabrotica balteatalarvae in the second stage and then placed in a plastics container. 6days later, the percentage reduction in population (% activity) isdetermined by comparing the number of dead larvae on the treated plantswith that on untreated plants.

Compounds of the Tables exhibit good activity in this test.

Example E-11 Action Against Heliothis virescens

Young soybean plants are sprayed with an aqueous emulsion spray mixturecomprising 100 ppm of test compound. After the spray-coating has dried,the plants are populated with 10 caterpillars of Heliothis virescens inthe first stage and then placed in a plastics container. 6 days later,the percentage reduction in population and the percentage reduction infeeding damage (% activity) are determined by comparing the number ofdead caterpillars and the feeding damage on the treated plants with thaton untreated plants.

Compounds of the Tables exhibit good activity in this test.

Example E-12 Action Against Spodoptera littoralis

Young soybean plants are sprayed with an aqueous emulsion spray mixturecomprising 100 ppm of test compound. After the spray-coating has dried,the plants are populated with 10 caterpillars of Spodoptera littoralisin the third stage and then placed in a plastics container. 3 dayslater, the percentage reduction in population and the percentagereduction in feeding damage (% activity) are determined by comparing thenumber of dead caterpillars and the feeding damage on the treated plantswith that on untreated plants,.

Compounds of the Tables exhibit good activity in this test.

E-13 Action Against Nilaparvata lugens

Rice plants are treated with an aqueous emulsion spray mixturecomprising 100 ppm of the test compound. After the spray-coating hasdried, the rice plants are populated with cicada larvae in the 2nd and3rd stages. The evaluation is carried out 21 days later. The percentagereduction in population (% activity) is determined by comparing thenumber of surviving cicadas on the treated plants with that on theuntreated plants.

The compounds of the Tables exhibit an activity exceeding 90%.

B-14 Action Against Plutella xylostella Caterpillars

Young cabbage plants are sprayed with an aqueous emulsion spray mixturecomprising 100 ppm of test compound. After the spray-coating has dried,the cabbage plants are populated with 10 caterpillars of Plutellaxylostella in the third stage and placed in a plastics container. Theevaluation is carried out 3 days later. The percentage reduction inpopulation and the percentage reduction in feeding damage (% activity)are determined by comparing the number of dead caterpillars and thefeeding damage on the treated plants with that on the untreated plants.

Compounds from the Tables exhibit a good activity.

Example E-15 Action Against Musca domestica

A sugar cube is so treated with a solution of the test compound that,after drying overnight, the concentration of test compound in the sugaris 250 ppm. The treated cube is placed on an aluminium dish togetherwith a wet cotton wool swab and 10 adult Musca domestica of anOP-resistant strain, covered with a glass beaker and incubated at 25° C.The mortality rate is determined 24 hours later.

Compounds from the Tables exhibit a good activity.

BIOLOGICAL EXAMPLES C. Acaricidal Action E-16 Action Against Tetranychusurticae

Young bean plants are populated with a mixed population of Tetranychusurticae and sprayed one day later with an aqueous emulsion spray mixturecomprising 400 ppm of test compound. The plants are then incubated for 6days at 25° C. and subsequently evaluated. The percentage reduction inpopulation (% activity) is determined by comparing the number of deadeggs, larvae and adults on the untreated plants with that on theuntreated plants.

Compounds from the Tables exhibit a good activity.

E-17 Action Against a Mixed Population of Tetranychus cinnabarinusSeries of Dilutions

Dwarf beans are populated at the 2-leaf stage with a mixed population(eggs, larvae/nymphs, adults) of an OP-tolerant Tetranychus cinnabarinusstrain. 24 hours after infestation, the products are applied to theplants in concentrations of 200, 100, 50 mg a.i./l in an automatic spraycabin. The substances are formulated and diluted to the correspondingconcentrations with water. The test is evaluated for percentagemortality of eggs, larvae/nymphs and adults 2 and 7 days after theapplication. Compounds of the Tables exhibit over 70% mortality indilutions up to 50 mg a.i./litre.

E-18 Action Against Boophilus microplus

Fully replete adult tick females are affixed to a PVC sheet, coveredwith a cotton wool swab, and 10 ml of an aqueous test solutioncomprising 125 ppm of test compound are poured on. The cotton wool swabis removed and the ticks are incubated for 4 weeks until oviposition hastaken place. The action is demonstrated either as mortality or sterilityin the females, or as ovicidal action in the eggs.

What is claimed is:
 1. A compound of formula I

wherein: X is CH or N; Y is O, S, S═O or NR₅; Z is OR₂, SR₂ or N(R₃)R₄;n is 0, 1, 2, 3, 4 or 5; or Y and Z together form a 5- to 7-memberedring having 2 or 3 hetero atoms O and/or N that is unsubstituted ormono- or poly-substituted by C₁-C₄alkyl, halo-C₁-C₄alkyl, halogen, ═O orby cyclopropyl; W is an aldimino or ketimino group selected from thegroup consisting of group a)

wherein R₁₁ and R₁₂ are each independently of the other hydrogen, cyano,C₁-C₁₂alkyl, halo-C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl,C₃-C₆cycloalkyl, cyclopropylmethyl, C₁-C₄alkoxy, C₂-C₁₂alkoxyalkyl,C₁-C₄alkoxycarbonyl, aminocarbonyl, C₁-C₄alkylaminocarbonyl,bis(C₁-C₄alkyl)aminocarbonyl, ureidocarbonyl, C₁-C₄alkylthio,C₂-C₅alkylthioalkyl; an unsubstituted or up to penta-substituted ringhaving a maximum of 15 ring carbon atoms that may be multi-membered andhas from 0 to 3 hetero atoms N, O and/or S, it being possible for thering to be bonded by a bridge having a maximum of 4 chain atoms and thatmay be linear or branched and may contain CO, oxygen or sulfur; or R₁₁and R₁₂ together with the common carbon atom are an unsubstituted or upto penta-substituted ring having a maximum of 15 ring carbon atoms thatmay be multi-membered and has from 0 to 3 hetero atoms N, O and/or S;the possible substituents of all of those groups mentioned for R₁₁ andR₁₂ individually or together being selected from C₁-C₄alkyl,C₂-C₄alkenyl, C₂-C₄alkynyl, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄haloalkyl,C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₁-C₄haloalkoxy, halogen, cyano,cyano-C₁-C₂alkyl, cyano-C₁-C₂alkoxy, oxo, thioxo, OH, NO₂, SCN,thiocyanomethyl, Si(CH₃)₃, NH₂, NH(C₁-C₄alkyl), N(C₁-C₄alkyl)₂,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylcarbonyl, C₁-C₄haloalkylcarbonyl,C₁-C₄alkoxycarbonyl, C₁-C₄haloalkoxycarbonyl, aminocarbonyl,C₁-C₄alkyl-aminocarbonyl, bis(C₁-C₄alkylamino)carbonyl,arylaminocarbonyl, arylaminothiocarbonyl, C₁-C₄haloalkylcarbonyloxy,C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxycarbonyloxy, aminocarbonyloxy,C₁-C₄alkylaminocarbonyloxy, bis(C₁-C₄alkylamino)carbonyloxy,arylaminocarbonyloxy, arylaminothiocarbonyloxy, C₁-C₄alkoximinomethyl,—CSNH₂, —SH, C₁-C₄alkylthiomethyl, C₂-C₄alkenyloxy, C₂-C₄alkynyloxy,C₂-C₄haloalkenyloxy, C₁-C₄alkylsulfinylmethyl, C₁-C₄alkylsulfonylmethyl,phenylsulfinylmethyl, phenylsulfonylmethyl, trifluoromethylsulfonyl,C₃-C₆cycloalkyl, phenyl, benzyl, phenoxy, phenylthio, benzyloxy andbenzylthio; it being possible for the aromatic groups to carry a maximumof 5 further substituents selected from halogen, C₁-C₄alkyl,C₁-C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, CN and NO₂, and it beingpossible for two adjacent substituents of the maximum of 5 substituentsto form an aliphatic bridge having a maximum of 5 members, which bridgehas from 0 to 2 oxygen atoms and 0 or 1 carbonyl group and may besubstituted a maximum of four times by halogen, C₁-C₄alkyl, C₁-C₄alkoxyand/or by a single phenyl group; or wherein

R₁₂ is a group e) wherein: R₁₃ is hydrogen, cyano, C₁-C₆alkyl,C₃-C₆cycloalkyl, C₁-C₆alkoxycarbonyl, heteroaryl, heterocyclyl,naphthyl, C₁-C₆alkoxy, aryloxy, heteroaryloxy, C₁-C₆alkylamino,bis(C₁-C₆alkyl)amino, arylamino or heteroarylamino, it being possiblefor all of the radicals mentioned other than cyano to be unsubstitutedor substituted by alkyl, alkoxy, haloalkyl, haloalkoxy, alkylthio,alkylsulfenyl, alkylsulfinyl, halogen, nitro, cyano, aryl, aryloxy,heteroaryl or by heteroaryloxy, or a group f)

wherein R₁₅ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy,halo-C₁-C₆alkoxy, halogen, C₃-C₆cycloalkyl unsubstituted or substitutedby from 1 to 5 halogen atoms, C₂-C₆alkenyl, halo-C₂-C₆alkenyl,optionally substituted C₃-C₆-alkynyl, cyano, cyano-C₁-C₂alkyl,cyano-C₁-C₂alkoxy, OH, NO₂, SCN, thiocyanomethyl, Si(CH₃)₃, NH₂,NH(C₁-C₄alkyl), N(C₁-C₄alkyl)₂, C₁-C₄alkoxymethyl,C₁-C₄haloalkylcarbonyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl,aminocarbonyl, C₁-C₄alkylaminocarbonyl, bis(C₁-C₄alkylamino)carbonyl,arylaminocarbonyl, arylaminothiocarbonyl, C₁-C₄alkoximinomethyl, —CSNH₂,—SH, C₁-C₄alkylthiomethyl, C₂-C₄alkenyloxy, C₂-C₄alkynyloxy,C₂-C₄haloalkenyloxy, C₁-C₄alkylsulfinylmethyl, C₁-C₄alkylsulfonylmethyl, phenylsulfinylmethyl, phenylsulfonylmethyl,trifluoromethylsulfonyl, C₃-C₆cycloalkyl, C₁-C₄haloalkylcarbonyloxy,C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxycarbonyloxy, aminocarbonyloxy,C₁-C₄alkylaminocarbonyloxy, bis(C₁-C₄alkylamino)carbonyloxy,arylaminocarbonyloxy, arylaminothiocarbonyloxy, aryl, heteroaryl orheterocyclyl; the aromatic groups in R₁₅ each independently of theothers being unsubstituted or mono- to penta-substituted by C₁-C₆alkyl,halo-C₁-C₆alkyl, halogen, C₁-C₆alkoxy or by halo-C₁-C₆alkoxy;tri(C₁-C₄alkyl)silyl or di(C₁-C₄alkyl)phenylsilyl; wherein when n isgreater than 1 the R₁₅ radicals may be identical or different; Q is adirect bond, C₁-C₈alkylene, C₂-C₆alkenylene, C₂-C₆alkynylene, O,O(C₁-C₆alkylene), (C₁-C₆alkylene)O, S(═O)p, S(═O)_(p)(C₁-C₆alkylene) or(C₁-C₆alkylene)S(═O)_(p); m is 0, 1, 2, 3, 4 or 5; p is 0, 1 or 2; andR₁₄ is hydrogen; C₁-C₆alkyl; C₁-C₆haloalkyl having from 1 to 15 halogenatoms; C₁-C₄-alkoxy-C₁-C₂alkyl; C₂-C₄alkenyl-C₁-C₂alkyl unsubstituted orsubstituted by from 1 to 3 halogen atoms; C₂-C₄alkynyl-C₁-C₂alkyl;C₃-C₆cycloalkyl unsubstituted or substituted by from 1 to 4 halogenatoms; C₃-C₆cycloalkyl-C₁-C₄alkyl unsubstituted or substituted by from 1to 4 halogen atoms; cyano-C₁-C₄alkyl; C₁-C₄alkoxycarbonyl-C₁-C₄alkyl;phenyl-C₁-C₃alkyl unsubstituted or substituted by halogen, C₁-C₃alkyl,C₁-C₄alkoxy, C₁-C₄haloalkyl, cyano, nitro and/or by C₁-C₄alkylenedioxyand wherein the phenyl group may be substituted by from 1 to 3 identicalor different substituents; phenyl unsubstituted or substituted by one ortwo substituents, which may be the same or different, selected fromC₁-C₄alkyl, C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3halogen atoms, nitro and cyano; or pyridyl unsubstituted or substitutedby one or two substituents, which may be the same or different, selectedfrom C₁-C₄alkyl, C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3halogen atoms, nitro and cyano; R₁ is cyclopropyl, C₁-C₆alkyl orhalo-C₁-C₆alkyl; R₂ and R₃ are each independently of the otherC₁-C₆alkyl or halo-C₁-C₆alkyl; R₄ and R₅ are each independently of theother hydrogen, C₁-C₆alkyl or C₁-C₆alkoxy; R₈ and R₉ are eachindependently of the other hydrogen or C₁-C₃alkyl; or R₈ and R₉ togetherare C₂-C₆alkenyl or C₃-C₆cycloalkyl; R₂₁ and R₂₂ are each independentlyof the other hydrogen, halogen, C₁-C₈alkyl, C₁-C₈alkoxy orC₁-C₈alkylthio; and R₂₃, R₂₄, R₂₅ and R₂₆ are each independently of theothers hydrogen, halogen, C₁-C₈alkyl or C₁-C₈alkoxy.
 2. A compoundaccording to claim 1 wherein: R₁ is methyl; R₂, R₃ and R₅ are eachindependently of the others C₁-C₂alkyl, and R₄ is hydrogen.
 3. Acompound according to claim 1 wherein: X is N; Y is O, S or S═O,preferably O; Z is OR₂, SR₂ or N(R₃)H; and R₂ and R₃ are C₁-C₂alkyl. 4.A compound according to claim 1 wherein: X is CH; Y is O, S or S═O, Z isOR₂; and R₂ is C₁-C₂alkyl.
 5. A compound according to claim 1 wherein Yand Z together are a group

wherein: A is unsubstituted or methyl-substituted alkanediyl having from1 to 3 carbon atoms; and R₆ is hydrogen, C₁-C₃alkyl, cyclopropyl or CF₃.6. A compound according to claim 1 wherein: R₈ and R₉ are hydrogen ormethyl; R₂₁ and R₂₂ are each independently of the other hydrogen,chlorine, bromine, C₁-C₄alkyl or C₁-C₄alkoxy; R₂₃, R₂₄, R₂₅ and R₂₆ arehydrogen; and n is0, 1 or
 2. 7. A compound according to claim 6 wherein:R₈ and R₉ are hydrogen; R₂₁ and R₂₂ are each independently of the otherhydrogen or methyl; and n is
 0. 8. A compound according to claim 1wherein: R₁₁ is hydrogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, cyclopropyl,C₁-C₄alkoxymethyl, C₁-C₄alkoxy, C₁-C₄alkylthio or cyano; and R₁₂ isphenyl or pyridyl each unsubstituted or substituted.
 9. A compoundaccording to claim 8 wherein: R₁₁ is C₁-C₄alkyl, cyclopropyl or cyano;and R₁₂ is phenyl unsubstituted or substituted by one or twosubstituents, which may be the same or different, selected fromC₁-C₄alkyl, C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3halogen atoms, C₂-C₄alkenyl, C₂-C₄alkynyl, nitro and cyano; or pyridylunsubstituted or substituted by one or two substituents, which may bethe same or different, selected from C₁-C₄alkyl, C₁-C₄alkoxy, halogen,C₁-C₂haloalkyl having from 1 to 3 halogen atoms, nitro and cyano.
 10. Acompound according to claim 1 wherein: R₁₁ is hydrogen, C₁-C₄alkyl,halo-C₁-C₄alkyl, cyclopropyl, C₁-C₄alkoxymethyl, C₁-C₄alkoxy,C₁-C₄alkylthio or cyano; and R₁₂ is a group e)


11. A compound according to claim 10 wherein: R₁₃ is hydrogen,C₁-C₆alkyl, C₃-C₆cycloalkyl, cyano or a group f)

wherein R₁₅ is C₁-C₆alkyl, halo-C₁-C₆alkyl, cyclopropyl unsubstituted orsubstituted by from 1 to 5 chlorine atoms, C₂-C₆alkenyl unsubstituted orsubstituted by from 1 to 3 halogen atoms, or unsubstituted orsubstituted C₃-C₆alkynyl; also phenyl unsubstituted or mono- topenta-substituted by C₁-C₆alkyl, halo-C₁-C₆alkyl, halogen, C₁-C₆alkoxyor by halo-C₁-C₆alkoxy; or pyridyl unsubstituted or mono- totetra-substituted by C₁-C₆alkyl, halo-C₁-C₆alkyl, halogen, C₁-C₆alkoxyor by halo-C₁-C₆alkoxy; Q is a direct bond, C₁-C₄alkylene, O,O(C₁-C₄alkylene) or (C₁-C₄alkylene)O, m is 0, 1 or 2; and R₁₄ ishydrogen; C₁-C₆alkyl; C₁-C₆haloalkyl having from 1 to 15 halogen atoms;C₁-C₄-alkoxy-C₁-C₂alkyl; C₂-C₄alkenyl-C₁-C₂alkyl unsubstituted orsubstituted by from 1 to 3 halogen atoms; C₂-C₄alkynyl-C₁-C₂alkyl;C₃-C₆-cycloalkyl unsubstituted or substituted by from 1 to 4 halogenatoms; C₃-C₆cycloalkyl-C₁-C₄alkyl unsubstituted or substituted by from 1to 4 halogen atoms; cyano-C₁-C₄alkyl; C₁-C₄alkoxycarbonyl-C₁-C₄alkyl;phenyl-C₁-C₃alkyl unsubstituted or substituted by halogen, C₁-C₃alkyl,C₁-C₄alkoxy, C₁-C₄haloalkyl, cyano, nitro and/or by C₁-C₄alkylenedioxywherein the phenyl group may be substituted by from 1 to 3 identical ordifferent substituents; phenyl unsubstituted or substituted by one ortwo substituents, which may be the same or different, selected fromC₁-C₄alkyl, C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3halogen atoms, nitro and cyano; or pyridyl unsubstituted or substitutedby one or two substituents, which may be the same or different, selectedfrom C₁-C₄alkyl, C₁-C₄alkoxy, halogen, C₁-C₂haloalkyl having from 1 to 3halogen atoms, nitro and cyano.
 12. A compound according to claim 1wherein: R₁₁ is methyl; R₁₂ is a group e)

R₁₃ is a group f)

wherein R₁₅ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy,halo-C₁-C₆alkoxy, halogen, C₃-C₆-cycloalkyl unsubstituted or substitutedby from 1 to 5 halogen atoms, C₂-C₆alkenyl, halo-C₂-C₆alkenyl,C₃-C₆alkynyl, cyano, cyano-C₁-C₂alkyl, cyano-C₁-C₂alkoxy, OH, NO₂, SCN,thiocyanomethyl, Si(CH₃)₃, NH₂, NH(C₁-C₄alkyl), N(C₁-C₄alkyl)₂,C₁-C₄alkoxymethyl, C₁-C₄haloalkylcarbonyl C₁-C₄alkylcarbonyl,C₁-C₄alkoxycarbonyl, aminocarbonyl, C₁-C₄alkylaminocarbonyl,bis(C₁-C₄alkylamino)carbonyl, arylaminocarbonyl, arylaminothiocarbonyl,C₁-C₄alkoximinomethyl, —CSNH₂, —SH, C₁-C₄alkylthiomethyl,C₂-C₄alkenyloxy, C₂-C₄alkynyloxy, C₂-C₄haloalkenyloxy,C₁-C₄alkylsulfinylmethyl, C₁-C₄alkylsulfonylmethyl,phenylsulfinylmethyl, phenylsulfonylmethyl, trifluoromethylsulfonyl,C₃-C₆cycloalkyl, C₁-C₄haloalkylcarbonyloxy, C₁-C₄-alkylcarbonyloxy,C₁-C₄alkoxycarbonyloxy, aminocarbonyloxy, C₁-C₄alkylaminocarbonyloxy,bis(C₁-C₄alkylamino)carbonyloxy, arylaminocarbonyloxy,arylaminothiocarbonyloxy, aryl, heteroaryl or heterocyclyl; wherein thearomatic groups in R₁₅ are each independently of the other unsubstitutedor mono- to penta-substituted by C₁-C₆alkyl, halo-C₁-C₆alkyl, halogen,C₁-C₆alkoxy or by halo-C₁-C₆alkoxy; Q is a direct bond, C₁-C₄alkylene,C₂-C₄alkenylene, C₂-C₄alkynylene, O, O(C₁-C₂alkylene) or(C₁-C₂alkylene)O; m is 0 or 1; and R₁₄ is methyl, ethyl or propargyl.13. A compound according to claim 10 wherein: R₁₃ is heteroaryl orheterocyclyl, which are each independently of the other unsubstituted ormono- to penta-substituted by C₁-C₆alkyl, halo-C₁-C₆alkyl, halogen,C₁-C₆alkoxy or by halo-C₁-C₆alkoxy.
 14. A compound according to claim 13wherein: R₁₃ is pyridyl, pyrimidinyl, imidazolyl, thiazolyl or pyrrolyleach unsubstituted or mono- to tri-substituted by methyl,halo-C₁-C₂alkyl, C₁-C₂alkoxy, halo-C₁-C₂alkoxy or by halogen.
 15. Acompound according to claim 2 wherein: at least one of R₂, R₃ and R₅ ismethyl.
 16. A compound according to claim 3 wherein Y is O.
 17. Acompound according to claim 3 wherein Z is OR₂ or SR₂.
 18. A compoundaccording to claim 3 wherein R₂ and R₃ are methyl.
 19. A compoundaccording to claim 4 wherein Y is O.
 20. A compound according to claim 4wherein R₂ is methyl.
 21. A compound according to claim 5 wherein A isunsubstituted or methyl-substituted dimethylene.
 22. A process for thepreparation of a compound of formula I according to claim 1, whichcomprises reacting a compound of formula II with a compound of formulaIII

wherein n, X, Y, Z, R₁, R₈, R₉, W and R₂₁ to R₂₆ are as defined forformula I.
 23. A compound of formula IV

wherein n, X, Y, Z, R₁, R₈, R₉ and R₂₁ to R₂₆ are as defined for formulaI according to claim 1 and L is a leaving group.
 24. A compound offormula XII

wherein n, X, Y, Z, R₁, R₈, R₉ and R₂₁ to R₂₆ are as defined for formulaI according to claim 1 and wherein R₃₁ and R₃₂ are each independently ofthe other C₁-C₆alkyl, C₁-C₆alkenyl, C₁-C₆alkoxyalkyl, C₃-C₆cycloalkyl orunsubstituted or substituted benzyl, or R₃₁ and R₃₂ together with thenitrogen atom are an unsubstituted or substituted 6- or 7-membered ringthat may have a further hetero atom O, S or N in addition to thenitrogen atom.
 25. A compound of formula XIV

wherein n, Y, Z, W, R₈, R₉ and R₂₁ to R₂₆ are as defined for formula Iaccording to claim
 1. 26. A process for the preparation of a compound offormula XIV which comprises reacting a compound of formula II with acompound of formula XIII

wherein n, Y, Z, R₈, R₉, W and R₂₁ to R₂₆ are as defined for formula Iaccording to claim
 1. 27. A composition for controlling pests,comprising as active ingredient an effective amount of a compoundaccording to claim 1 together with a suitable carrier.
 28. A method forthe control and prevention of pests, which comprises applying a compoundaccording to claim 1 to the pests or to the locus thereof.
 29. A methodaccording to claim 28, wherein the pests are phytopathogenic fungi. 30.A method according to claim 28, wherein the pests are insects orAcarina.
 31. A method according to claim 28, wherein seed is treated.